Haloacetamidines and the herbicidal use thereof

ABSTRACT

Dichloroacetamidines having the formula ##STR1## in which A and B are independently selected from hydrogen, fluorine, chlorine, bromine and methyl, provided that at least one of A or B is other than hydrogen; 
     M is hydrogen or methyl; 
     X is selected from the group consisting of trifluoromethyl, lower alkyl, nitro, chloro, bromo, fluoro, cyano, lower alkoxy acetyl, lower alkylthio, trifluoromethylthio, and 3,3-diloweralkyl ureido; 
     Y is selected from the group consisting of hydrogen, lower alkyl, chloro, fluoro, nitro, trifluoromethyl, and lower alkoxy; 
     Z is selected from the group consisting of hydrogen and chloro; 
     R 1  is selected from the group consisting of hydrogen, alkyl and allyl; 
     R 2  is selected from the group consisting of alkyl, allyl, benzyl, hydroxyalkyl, alkynyl, N-alkyl amido, alkoxyalkyl, dialkoxyalkyl, alkoxy, cyano alkyl, substituted phenyl wherein the substituent is selected from the group trifluoromethyl, dichloro and 3,3-dimethylureido; and 
     R 1  and R 2  taken together with the nitrogen is selected from the group consisting of alkyl substituted oxazolidyl, morpholinyl, piperidinyl and pyrrolidinyl; and salts thereof; useful as herbicides.

CROSS-REFERENCE TO RELATED APPLICATIONS

This is a continuation-in-part of Ser. No. 512,862 filed Jul. 11, 1983, which is a continuation of Ser. No. 272,860 filed Jun. 12, 1981, which is a continuation-in-part of Ser. No. 091,854 filed Nov. 6, 1979 all now abandoned.

This invention relates to certain novel haloacetamidines which are useful as herbicides. More specifically, this invention relates to a novel herbicidal compound known as acetamidines, more particularly dichloroacetamidines.

BACKGROUND OF THE INVENTION

1. Use of Herbicides

An herbicide is a compound which controls or modifies plant growth, e.g., killing, retarding, defoliating, desiccating, regulating, stunting, tillering, stimulating, and dwarfing. "Plant" refers to all physical parts, including seeds, seedlings, saplings, roots, tubers, stems, stalks, foliage, and fruits. "Plant growth" is meant to include all phases of development from seed germination to natural or induced cessation of life.

Herbicides are generally used to control or eradicate weed pests. They have gained a high degree of commercial success because it has been shown that such control increases crop yield and reduces harvesting costs.

Herbicidal effectiveness is dependent upon several variables. One of these is the time or growth related method of application. The most popular methods of application include: pre-plant incorporation into the soil; pre-emergence surface treatment of seeded soil; and post-emergence treatment of the plant and soil.

The most important determinant of herbicidal effectiveness is the susceptibility of the target weed. Certain herbicidal compounds are phytotoxic to some weed species but not to others.

The manufacturer of the herbicide recommends a range of rates and concentrations calculated to maximize weed control. The range of rates varies from approximately 0.01 to 50 pounds per acre, usually from 0.1 to 25 pounds per acre. The actual amount used depends upon several considerations including particular weed susceptibility and overall cost limitations.

2. Prior Art

U S. Pat. No. 3,153,670 relates primarily to vinyl amines. A utility disclosed for the vinyl amines is the preparation of amidines from primary amines. In U.S. Pat. No. 3,153,670 the following specific compounds are disclosed: N,N-diethyl-N'-phenyl 2,2-dichloroacetamidine, N,N-diethyl-N'-tolyl 2,2-dichloroacetamidine, N,N-diethyl-N'-p-chlorophenyl 2,2-dichloroacetamidine, N,N-diethyl-N'-p-nitrophenyl 2,2-dichloroacetamidine, and N,N-diethyl-N'-p-ethoxyphenyl 2,2-dichloroacetamidine. U.S. Pat. No. 3,153,670 generically discloses herbicidal utility for the above compounds. No specific testing or method of testing for herbicidal activity is set forth in the cited patent.

The J. Am. Chem. Soc. 82 902-9 (1960) discloses the compound N,N-diethyl-N'-phenyl 2,2-dichloroacetamidine.

U.S. Pat. No. 3,576,618 discloses certain N-trichloroacetamidines having the formula ##STR2## These compounds are useful as herbicides. The form taken by the compounds are the aryl amino form, thereby allowing only one substituent on the aryl amino nitrogen and always a hydrogen on the amino nitrogen with the phenyl moiety. These are commonly known as "reverse" acetamidines.

Similarly, West German Offenlegungschrift No. 2557651 relates to N-aryl-2,2-dihalo-acetamidine derivatives of the general formula ##STR3## wherein R¹, R² and R³ are the same or different and are defined as a hydrogen, halogen atom, aliphatic moiety or R⁴ --O-- wherein R⁴ is aliphatic or aromatic moiety and X is a halogen atom. These acetamidines are termed "reverse" acetamidines because of the tautomeric system within the molecule. The utility is disclosed as fungicidal.

The following are a group of patents which relate to acetamidines in which the two (2) positions substituted with a non-halogenated methyl group: U.S. Pat. No. 3,284,289, U.S. Pat. No. 3,487,156, U.S. Pat. No. 3,781,356, U.S. Pat. No. 3,781,357, U.S. Pat. No. 3,803,134 and U.S. Pat. No. 3,867,448.

The compounds disclosed in the above-cited U.S. patents are taught to be useful for the control of acarids and insects, combating undesired plant growth, harmful micro-organism, nematodes.

U.S. Pat. No. 3,428,681 relates to N-halotrichloroacetamidines having the general formula ##STR4## wherein X is chlorine, iodine or bromine and each R is independently selected from the group consisting of hydrogen, alkyl, aryl, cycloalkyl and heterocyclic. These compounds are disclosed as useful as bleaches and disinfectants, effective as fungicidal, herbicidal and algaecidal agents.

It is recognized the amidine compounds have the potential of existing in two geometrical isomeric forms, known as tautomers, in the aryl imino form [ArN═C(NHR)] and the aryl amino form [ArN═C(NR)]. Many compounds containing an "amidine moiety" possess potential for tautomerism, geometrical isomerism and conformational change. The "amidine moiety" refers to compounds containing the potentially tautomeric system --NH--C(X)═N-- in which X is C, N, O or S as described by Jackman, L. M. et al., J. Am. Chem. Soc. 97 (10) 2811-18. In the present application the predominant tautomer is presumed to be in the imino form and the representation of the dichloro acetamidines will be in this form.

DESCRIPTION OF THE INVENTION

The compounds comprising the instant class of compound corresponds to the general formula ##STR5## in which A and B are independently selected from the group consisting of hydrogen, fluorine, chlorine, bromine and methyl, provided that at least one of A or B is other than hydrogen; m is hydrogen or methyl;

X is selected from the group consisting of trifluoromethyl, lower alkyl, nitro, chloro, bromo, fluoro, cyano, lower alkoxy acetyl, lower alkylthio, trifluoromethylthio, and 3,3-diloweralkyl ureido;

Y is selected from the group consisting of hydrogen, lower alkyl, chloro, fluoro, nitro, trifluoromethyl, and lower alkoxy;

Z is selected from the group consisting of hydrogen, and chloro;

R₁ is selected from the group consisting of hydrogen, alkyl, and allyl;

R₂ is selected from the group consisting of alkyl, allyl, benzyl, hydroxyalkyl, alkynyl, N-alkyl amido, alkoxyalkyl, dialkoxyalkyl, alkoxy, cyano alkyl, substituted phenyl wherein the substituent is selected from the group trifluoromethyl, dichloro and 3,3-dimethylureido; and

R₁ and R₂ taken together with the nitrogen is selected from the group consisting of alkyl substituted oxazolidyl and alkyl substituted thiazolidyl, morpholinyl, piperidinyl and pyrrolidinyl; and salts thereof.

More particularly, with reference to the general formula above:

A, B and M are as defined and X is selected from the group consisting of trifluoromethyl, lower alkyl having 1 to 3 carbon atoms, inclusive, nitro, chloro, bromo, fluoro, cyano, lower alkoxy having 1 to 3 carbon atoms, inclusive, acetyl, lower alkylthio having 1 to 3 carbon atoms, inclusive, trifluoromethylthio and 3,3-diloweralkyl ureido in which each lower alkyl has from 1 to 2 carbon atoms, inclusive;

Y is selected from the group consisting of hydrogen, lower alkyl having 1 to 3 carbon atoms, inclusive, chloro, fluoro, nitro, trifluoromethyl and lower alkoxy having 1 to 3 carbon atoms, inclusive;

Z is selected from the group consisting of hydrogen and chloro;

R₁ is selected from the group consisting of hydrogen, alkyl having 1 to 6 carbon atoms, inclusive, and allyl;

R₂ is selected from the group consisting of alkyl having 1 to 6 carbon atoms, inclusive, allyl, benzyl, hydroxyethyl, alkynyl having 3 to 4 carbon atoms, inclusive, N-alkylamido in which the alkyl has 1 to 3 carbon atoms, inclusive, alkoxyalkyl having 2 to 6 carbon atoms, inclusive, dialkoxyalkyl having 3 to 6 carbon atoms, inclusive, alkoxy having 1 to 4 carbon atoms, inclusive, cyanoalkyl having 2 to 4 carbon atoms, inclusive, substituted phenyl wherein said substituent is selected from the group trifluoromethyl, dichloro and 3,3-dimethylureido; and

R₁ and R₂ taken together with the nitrogen is selected from the group consisting of alkyl substituted oxazolidyl and alkyl substituted thiazolidyl wherein said oxazolidyl or thiazolidyl is substituted 1, 2 or 3 times with alkyl having from 1 and 3 carbon atoms, inclusive, morpholinyl, piperidinyl and pyrrolidinyl; and

salts thereof with an acid selected from the group consisting of HCl, HBr, HI, HF, H₂ SO₄, CC1₃ COOH, 2,4-dichlorophenoxy acetic acid, 3-amino-2,5-dichlorobenzoic acid, hexanoic acid, stearic acid, naphthalene acetic acid, pivalic acid, succinic acid, 10-undecenoic acid, benzoic acid, maleic acid and malonic acid.

The terms "lower alkyl" and "alkyl" includes straight chain and branched chain substituents of this type; the term "lower alkoxy" includes straight chain and branched chain substituents of this type; the term "alkynyl" includes substituents of this type having straight or branched chain and at least one triple bond; the terms "alkoxy alkyl" and "dialkyloxy alkyl" include substituents of this type having a straight or branched chain configuration, and cyanoalkyl includes substituents having at least one cyano group (CN) and alkyl in straight or branched chain.

The compounds of this invention have been found to be active herbicides., that is, the compounds have been found to be herbicidally active against various species of weeds. In the broadest sense, the term "weeds" refers to plants which grow in locations in which they are not desired. As will be seen from the data which follows, these compounds show various activities as pre-emergence and/or post-emergence herbicides. In some cases they have been found to show particular activity against certain weed species.

This invention, therefore, also relates to a method of controlling undesirable vegetation comprising applying to such vegetation or the locus where such vegetation is found, a herbicidally effective amount of a compound as described herein, and also relates to herbicidal compositions of matter comprising a herbicidally effective amount of a compound as described herein plus an inert diluent or carrier suitable for use with herbicides.

As used herein, the term "herbicide" means a compound which controls or modifies the growth of plants, particularly of undesirable plants. By the term "herbicidally effective amount" is meant an amount of a compound which causes a controlling or modifying effect on the growth of treated plants. The term "plants" is meant to include germinant seeds, emerging seedlings and established vegetation including roots and the above ground portions. Such modifying and controlling effects include all deviations from natural development, for example, killing, retardation, defoliation, desiccation, regulation, stunting, tillering, stimulation, dwarfing and the like.

In general, the compounds of the present invention can be prepared by the following methods:

I. An appropriate substituted aniline (1) is reacted with an acyl chloride (2) to produce corresponding substituted anilide (3). The anilide is chlorinated with phosphorus chloride to prepare the substituted phenyl containing imidoyl chloride (4). A subsequent reaction with a secondary amine (4a) produces a substituted acetamidine (5) of the present invention. This sequence of reactions is depicted by the following equations: ##STR6## wherein A, B, M, R₁, R₂, X, Y and Z have the same significance as previously defined.

REACTION SCHEME I

II. An alternative reaction scheme is the reaction of an acylchloride (6) with a primary amine (7) to produce the corresponding amide (8). This reaction is followed by treatment of the amide (8) with phosphorus pentachloride in phosphorus oxychloride as a solvent to produce the imidoyl chloride (9). The imidoyl chloride is reacted with a substituted aniline to produce the substituted acetamidine (11a) or (11b) of the present invention. This sequence of reactions is depicted by the following equations: ##STR7## wherein A, B, M, R₁, R₂, X, Y and Z have the same significance as previously defined.

REACTION SCHEME II

In reaction schemes I and II, some of the individual reactions are performed in the presence of an organic solvent, such as acetone, methylene chloride and the like, where good chemical practice dictates. The reaction temperatures can vary from -20° C. to 150° C. In many instances the reaction was exothermic. The reaction pressure may be atmospheric, subatmospheric or superatmospheric. However, for convenience of conducting the reactions, the pressure is generally atmospheric. The reaction time will, of course, vary depending upon the reactants and reaction temperature. Generally, the reaction time is from 0.25 to 24 hours, depending upon the steps and rate of reaction. After the reaction is complete, the product is recovered by separation from the by-products and the solvent removed as by evaporation, or distillation. The structure is confirmed hy nuclear magnetic resonance or infrared spectra.

The following are representative illustrative examples for the preparation of the compounds of the present invention and requisite intermediates therefor. Following the examples is a table of compounds which are prepared according to the described procedures.

EXAMPLE A Intermediate Preparation 3',5'-Dichloro-dichloroacetanilide

81 grams (0.5 mole) 3,5-dichloroaniline was dissolved in a flask containing 250 milliliters of reagent grade acetone. The solution was cooled to 0° C. and 74 grams (0.5 mole) dichloroacetyl chloride was added dropwise with vigorous stirring with the rate of addition adJusted to maintain the reaction temperature below 5° C.

When the addition was complete, 51 grams (0.50 mole) of triethylamine was immediately added dropwise with vigorous stirring, the addition rate adJusted to maintain the reaction temperature below 5° C. The reaction mixture was then allowed to attain ambient temperature and stirred at that temperature for one hour. The mixture was poured into water, the solid product filtered off and dried giving 126 grams (92.3% yield) of the desired product, a white. solid, m.p. 1323°-135° C.

EXAMPLE B Intermediate Preparation 3',5'-Dichlorophenyldichloroacetimidoyl chloride

of 121 grams (0.44 mole) 3',5'-dichloro-dichloroacetanilide and 100 milliliters of phosphorous oxychloride were combined. Phosphorous pentachloride, 92.5 grams (0.44 mole), was added and the mixture was stirred virorously with heating at reflux until hydrogen chloride evolution ceased. The phosphorous oxychloride was stripped off at reduced pressure. Distillation gave 109.8 grams (85% yield) of 3',5'-dichlorophenyldichloroacetimidoyl chloride containing a small amount of solid. The b.p was 122°-126°/0.03 millimeters.

EXAMPLE 1A N-3',5'-Dichlorophenyl-N'-isopropyldichloroacetamidine

10,2 grams (0.035 mol) 3',5'-dichlorophenyldichloroacetimidoyl chloride was dissolved in a flask containing 25 milliliters of methylene chloride and the solution cooled in an ice bath. 4.5 grams (0.076 mole) isopropyl amine was added dropwise while stirring vigorously and temperature maintained below 15° C. The reaction mixture was stirred at ambient temperature one hour, and washed with 100 milliliters water. The organic layer was separated, dried over magnesium sulfate and stripped at reduced pressure to yield 10.7 grams (97.3% yield) of N-3',5'-dichlorophenyl-N'-isopropyldichloroacetamidine, n_(d) ³⁰ 1.5653.

EXAMPLE C Intermediate Preparation N-Isopropyldichloroacetamide

Dichloroacetyl chloride, 442.5 grams (3.0 mole), was dissolved in a flask containing 900 milliliters of methylene chloride and the solution cooled to 0° C. in an ice/acetone bath. 354 grams (5.98 mole) of isopropyl amine was added dropwise with vigorous stirring and the addition rate was adjusted to maintain the reaction temperature below 5° C. When the addition was complete, the mixture was allowed to stir at ambient temperature for one hour then washed with 2×500 milliliters water, the organic phase separated, dried over magnesium sulfate and stripped of solvent at reduced pressure giving 499 grams (98% yield) of the desired product, a white solid, m.p. 45°-48° C.

EXAMPLE D Intermediate Preparation N-Isopropyldichloroacetimidoyl chloride

N-isopropyldichloroacetamide, 249.5 grams (2.94 mole), and 210 milliliters of phosphorous pentachloride, 306.5 grams (2.94 mole), was added and the mixture was stirred vigorously and heated at reflux until hydrogen chloride evolution ceased. The phosphorous oxychloride was stripped off at reduced pressure. Distillation at 4.5 millimeters gave 360 grams (65% yield) of N-isopropyldichloroacetimidoyl chloride, b.p. 63°-72° C.

EXAMPLE 1B Preparation via N-isopropyldichloroacetimidoyl chloride N-3',5'-Dichlorophenyl-N'-isopropyldichloroacetamidine

10.5 grams (0.065 mole) of 3,5-dichloroaniline was combined with 14.7 grams (0.078 mole) of N-isopropyl dichloroacetimidoyl chloride in a flask and heated to 30° C. The reaction proceeded to 48° C. and was heated again until it showed an exotherm. External heating was stopped and the reaction allowed to continue until it reached a peak exotherm of 150° C. and then allowed to cool to ambient temperature. While this reaction cooled, a second reaction using the same amounts and reagents was performed. This reaction was externally heated to 50° C. when it began to exotherm. A peak temperature of 140° C. was reached while the reaction flask was in an ice water bath. Both reaction mixtures were slurried in acetone, combined and diluted with ether and the solid hydrochloride filtered off. This yielded 42.2 grams (92.7% yield) of solid m.p. 201°-202° C. The entire amount was treated with 200 milliliters of 10% sodium hydroxide, extracted with 2×250 milliliters methylene chloride, the organic layer dried over magnesium sulfate and stripped of solvent under reduced pressure to give 36.5 grams (89% total yield) of an oil, n_(D) ³⁰ of 1.5672.

EXAMPLE 2 N-3',5'-Dimethylphenyl-N'-isopropyldichloroacetamidine

3,5-dimethyl aniline, 8.9 grams (0.073 mole), and N-isopropyl dichloroacetimidoyl chloride, 15.8 grams (0.084 mole), were combined in a flask and the temperature immediately rose to 35° C. An ice bath was applied, and when the temperature reached 45° C., acetone was added to the bath. The exotherm ceased at 115° C., the ice bath was removed and the flask heated to 120° C. and maintained at that temperature until the mixture seemed homogeneous. A second reaction was run in the same manner, both were allowed to cool, slurried in ether, combined and filtered off as the solid hydrochloride m.p. 201°-203° C. The hydrochloride was then treated with 10% sodium hydroxide, extracted with methylene chloride and the organic phase dried over magnesium sulfate and the solvent stripped off at reduced pressure to give 33.1 grams (82.8% yield) of the desired produce with an n_(D) ³⁰ 1.5382.

EXAMPLE 3 N-2,3-Dichlorophenyl-N'-isopropyldichloroacetamidine

9.7 grams (0.06 mole) of 2,3-dichloroaniline was combined with 13.6 grams (0.072 mole) N-isopropyldichloroacetimidoyl chloride and heated until the mixture started to exotherm. An ice bath was used to control but not stop, the exotherm. After the exotherm peaked, the flask and its contents were allowed to cool to ambient temperature and combined with a second reaction which was run in the same manner. These combined reactions were slurried in acetone, diluted with ether and the solid hydrochloride filtered off. The solid was then treated with 10% sodium hydroxide, extracted with methylene chloride, separated and the organic phase dried over magnesium sulfate. The solvent was then stripped off at reduced pressure to give 31.1 grams (82.7% yield) of the desired produce, an oil, n_(D) ³⁰ 1.5668.

EXAMPLE 4 N-3-Chloro-2-methylphenyl-N'-isopropyldichloroacetamidine

3-chloro-2-methylaniline, 10 grams (0.035 mole), and N-isopropyldichloroacetimidoyl chloride, 7.9 grams (0.042 mole), were combined in a flask, heated to initiate the reaction and the rate of exotherm controlled, but not stopped, with the application of an ice bath. After the exotherm subsided, the reaction flask was allowed to cool to ambient temperature and the contents slurried with acetone diluted with ether. The solid product was filtered off giving 10.0 grams (97.7% yield) of the hydrochloride which decomposed at 236° C. 5 grams (0.015 mole) of this hydrochloride was treated with 10% sodium hydroxide to give 4.3 grams (0.014 mole) of an oil, n_(D) ³⁰ 1.5440.

EXAMPLE 5 N-m-Trifluoromethylphenyl-N'-allyldichloroacetamidine

Allyl amine, 3 grams (0.053 mole), was dissolved in a flask containing 25 milliliters of methylene chloride. Meta-trifluoromethylphenyl dichloroacetimidoyl chloride, 7.6 grams (0.026 mole), was added dropwise while stirring and maintaining ambient temperature with a water bath. The mixture was allowed to stir one houre, washed with water, the organic phase separated and dried over magnesium sulfate and the solvent stripped at reduced pressure to give 6.9 grams (85.2% yield) of an oil, n_(D) ³⁰ 1.4986.

EXAMPLE 6 N-m-Trifluoromethylphenyl-N',N'-tetramethylenedichloroacetamidine

Pyrrolidine, 3.6 grams (0.051 mole), was combined in a with 25 milliliters of methylene chloride. Metatrifluoromethylphenyl dichloroacetimidoyl chloride, 7.3 grams (0.025 mole), was added dropwise while stirring and maintaining ambient temperature with a water bath. The mixture was allowed to stir one hour at ambient temperature, washed with water, the organic layer dried over magnesium sulfate and stripped of solvent to give 8.0 grams (98.8% yield) of an oil n_(D) ³⁰ 1.5140

EXAMPLE 7 4-(N-m-Trifluoromethylphenyl dichloroacetimidoyl) morpholine

Morpholine, 4.2 grams (0.0482 mole), was combined in a flask with 25 milliliters of methylene chloride. Metatrifluoromethylphenyl dichloroacetimidoyl chloride, 7 grams (0.024 mole), was added dropwise while stirring and maintaining ambient temperature with a water bath. The mixture was allowed to stir at ambient temperature one hour, then washed with water, the organic phase separated, dried over magnesium sulfate and the solvent stripped off at reduced pressure to give 7.3 grams (89% yield) of an oil, _(D) ³⁰ 1.5184.

EXAMPLE 8 (N-m-Trifluoromethylphenyl dichloroacetimidoyl 2,2,5-trimethyl oxazolidine

Twenty-two milliliters (0.048 mole) of a solution of 2,2,5-trimethyl oxazolidine in benzene (4 milliliters=1 gram in benzene) was combined in a flask with 15 milliliters liters of methylene chloride. Meta-trifluoromethylphenyl dichloroacetimidoyl chloride, 6.7 grams (0.023 mole), was added dropwise while stirring and maintaining ambient temperature with a water bath. The mixture was allowed to stir at ambient temperature one hour, washed with water, the organic layer separated, dried over magnesium sulfate and stripped of solvent to give 6.5 grams (76.5% yield) of an oil, n_(D) ³⁰ 1.4818.

EXAMPLE 9 Preparation of Intermediate N-Isopropyl chlorofluoroacetamide

A solution of 11.8 grams (0.2 mole) isopropyl amine in 20 milliliters ethyl alcohol were added dropwise at 10°-15° C. with stirring to a solution of ethyl fluorochloroacetate and 5 drops of ethylene glycol in 80 milliliters ethyl alcohol. The solution was stirred at 10°-20° C. for 2 hours and was then stored at -15° C. for 3 days. At this time, the solution was evaporated to leave a liquid, 25.2 grams, n_(D) ³⁰ 1.4395, identified as the title compound by infrared and nuclear magnetic resonance spectroscopy.

Preparation of Intermediate N-Isopropyl chlorofluoroacetamide

In a 100 milliliter flask were placed 22 grams (0.14 mole) of N-isopropyl chlorofluoroacetamide and 3 milliliters of phosphorous oxychloride. Pulverized phosphorous pentachloride, 30.0 grams (0.14 mole), was added to this mixture at an initial temperature of 32° C. The temperature rose to 42° C. over the course of the addition. After all the phosphorous pentachloride had been added, the mixture was heated. The maJority of the hydrogen chloride was evolved at 40° C. and by the time the temperature reached reflux (120° C.), gas evolution had ceased. The mixture was next distilled at atmospheric pressure using a 15 centimeter glass - helix packed column with attached variable takeoff condenser to give 17.8 grams of product, b.p. 136°-138° C., identified as the title compound by infrared and nuclear magnetic resonance spectroscopy.

N-(3,5-Dimethylphenyl)-N'-isopropyl chlorofluoroacetamidine

In a 100 milliliter flask was placed 5.0 grams (0.03 mole) of N-isopropylchlorofluoroacetimidoyl chloride. A thermometer and air-cooled condenser were attached to the flask. To this was added 2.8 grams (0.02 mole) of 3,5-dimethylaniline. There was an immediate increase in temperature and formation of a white solid. When the temperature reached 70° C., a cold bath was applied to moderate the reaction and when no further isotherm was observed, the mixture was heated to 140° C. with a heat-gun.

The mixture was then allowed to return to room temperature and the resulting dark oil was taken up in acetone, addition of pentane caused a solid to separate which was removed by filtration. This solid was mixed with 50 mililiters methylene chloride and shaken with 50 milliliters of 10% sodium hydroxide. The organic layer was separated, washed twice with 50 milliliters portion of water and dried over magnesium sulfate.

Removal of solvent in vacuum left an oil, 3.6 grams, n_(D) ³⁰ 1.5229, which was identified by infrared and nuclear magnetic resonance spectroscopy to be the title compound. The oil eventually crystallized to a solid of m.p. 37°-40° C.

EXAMPLE 10 N-(2,3-Dichlorophenyl)-N'-isopropyl chlorofluoroacetamidine

The above procedure was repeated with 5.0 grams (0.03 mole) N-isopropylchlorofluoroacetimidoyl chloride and 3.7 grams (0.02% mole) of 2,3-dichloroaniline to yield 3.7 grams of a dark oil, identified by infrared and nuclear magnetic resonance spectroscopy to be the title compound.

EXAMPLE 11 N-(3,5-Dichlorophenyl)-N'-isopropyl chlorofluoroacetamidine

The above procedure was repeated with 5.0 grams (0.03 mole) N-isopropylchlorofluoroacetimidoyl chloride and 3.7 grams (0.02 mole) of 3,5-dichloroaniline to yield 4.9 grams of an oil, n_(D) ³⁰ 1.5540, identified by infrared and nuclear magnetic resonance spectroscopy as the title compound.

EXAMPLE 12 Preparation of Intermediate N-Isopropylbromofluoro acetamide

A solution of 14.8 grams (0.25 mole) isopropyl amine in 25 milliliters ethanol was added dropwise to a solution of ethyl bromofluoroacetate, 40 grams (0.22 mole), and 5 drops ethylene glycol in 100 milliliters ethyl alcohol at 10°-15° C. The solution was stirred at 10°-20° C. for 2 hours and was then stored at -15° C. for 3 days. At this time, the solution was evaporated to leave a liquid, 41.8 grams, n_(D) ³⁰ 1,4629, identified by infrared spectroscopy as the title compound.

Preparation of Intermediate N-Isopropylbromofluoroacetimidoyl bromide

In a 100 milliliter flask fitted with a gas-inlet, thermometer, magnetic stirrer and reflux condenser were placed 20.0 grams (0.1 mole) of N-isopropylbromofluoroacetimidoyl bromide. Argon was flushed through the system and after 15 minutes, 27.3 grams (0.1 mole) of phosphorous tribromide were added in one portion. The temperature rose to 48° C. Cooling was applied with an ice bath and bromide, 1.1 grams (0.1 mole) was added slowly with stirring. After addition was complete, the mixture was allowed to come to room temperature and after one hour it was heated to 85°-90° C. The argon purge was maintained throughout the heating period. After 11/2 hours the evolution of HBr had ceased and the mixtrue was cooled to 10° C. and filtered free of phosphorous oxybromide. The filtrate was vacuum distilled to yield 16.4 grams, b.p. 53°-60° C. at 1 millimeter. Identified by infrared spectroscopy as the title compound.

N-(3,5-Dichlorophenyl)-N'-isopropyl bromofluoroacetamidine

In a 100 milliliter flask was placed 5.0 grams (0.02 mole) of the above imidoyl bromide. A thermometer and air cooled condenser were attached to the flask. To this was added 3.1 grams (0.02 mole) of 3,5-dichloroaniline. The temperature rose slowly to 70° C., and at 70° C. an ice bath was used to moderate the reaction. When no further exotherm was observed, the mixture was heated to 135° C. and was then allowed to cool. The residue was taken up in 50 milliliters methylene chloride and this solution was carefully shaken with 50 milliliters of 10% sodium hydroxide solution. The organic layer was then shaken with 50 milliliters of a saturated salt solution and dried. Removal of solvent in vacuum left an oil, 2.9 grams, identified by infrared and nuclear magnetic resonance spectroscopy as the title compound.

EXAMPLE 13 Preparation of Intermediate N-Isopropyldifluoroacetamide

A solution of 20 grams (0.16 mole) of ethyl difluoroacetate in 20 milliliters ethyl alcohol was added slowly in a solution of 9.5 grams (0.16 mole) isopropylamine amine and 5 drops of ethylene glycol in 30 milliliters ethyl alcohol. The temperature rose slowly to 27° C. The mixture was then refluxed for 3 days. After this reflux period, the solution was evaporated at 100 millimeters and the residue was distilled at atmospheric pressure to yield 18.0 grams, b.p. 86°-88°, identified by infrared spectroscopy as the title compound.

N-Isopropyldifluoroacetimidoyl bromide

In a 100 milliliter flask fitted with thermometer, gas-inlet, and magnetic stirrer was placed 12.0 grams (0.09 mole) of N-isopropyldifluoroacetamide. Argon was flushed through the system and phosphorous tribromide, 27.3 grams (0.09 mole), was added slowly at 10°-15° C. Bromine, 14.0 grams (0.09 mole), was then added slowly at 10°-15° C. with stirring. After all the bromine was added, the mixture was allowed to come to room temperature and was then heated with argon sweep at 85°-90° C. Heating was continued for 2 hours. The mixture was next cooled to 0° C. and filtered free of phosphorous oxybromide. The filtrate was vacuum distilled to yield 4.0 grams, b.p. 34°-38° (50 millimeters identified by infrared spectroscopy as the title compound.

N-(3,5-Dichlorophenyl)-N-isopropyldifluoroacetamidine

A solution of 3.2 grams (0.02 mole) of 3,5-dichloroaniline in 50 milliliters toluene was heated to reflux (111° C.) and 4.0 grams (0.02 mile) of N-isopropyldifluoroacetimidoyl bromide was added slowly. A vigorous reaction occurred with separation of solid. The mixture was refluxed for 1/2 hour after addition was complete, cooled and filtered to give 6.0 grams of the hydrobromide salt. The solid was slurried in 50 milliliters methylene chloride in a separatory funnel and this mixture was shaken with cold 5% sodium hydroxide solution. The mixture was phase-separated and washed with two 50 milliliter portions of water. Evaporation of solvent after drying left 3.9 grams of a liquid, n_(D) ³⁰ 1.5425, identified by infrared and nuclear magnetic resonance spectroscopy as the title compound.

Dichloroacetamidine Salt Examples EXAMPLE 14 Trifluoroacetic Acid Salt of N-(3,5-Dichlorophenyl)-N'-isopropyl dichloroacetamidine

The amidine (3.1 grams, 0.01 mole) and the trifluoroacetic acid (1.1 grams, 0.01 mole) were combined in 35 milliliters ethyl ether and the mixture allowed to stir overnight at room temperature, refluxed for 45 minutes and the solvent removed in vacuo. The product was a very viscous semi-solid. Yield: 2.0 grams (47.6%). Infrared indicated the product was the expected salt.

EXAMPLE 15 Composition of Pivalic Acid and N-(3,5-Dichlorophenyl-N'-isopropyl dichloroacetamidine

The amidine (3.1 grams, 0.01 mole) and pivalic acid (1.0 grams, 0.1 mole) were combined in 35 milliliters tetrahydrofuran. The mixture was stirred 1/2 hour at room temperature and refluxed 2 hours. The solvent was removed giving a tan oil, n_(D) ³⁰ 1.5192. Yield: 4.0 grams (97.5%). Infrared indicated a composition of pivalic acid and amidine.

EXAMPLE 16 Composition of 10-Undecenoic Acid and N-(3,5-Dichlorophenyl)-N'-isopropyl dichloroacetamidine

Same procedure as in Example 15. There was obtained a tan oil, n_(D) ³⁰ 1.5163. Yield: 4.5 grams (91.8%). Infrared confirmed the expected title composition.

EXAMPLE 17 Composition of Succinic Acid and N-(3,5-Dichlorophenyl)-N'-isopropyl dichloroacetamidine

Same procedure as in Example 15 using the acetamidine (3.1 grams, 0.01 mole) and succinic acid (0.6 grams, 005 mole). Viscous semi-solid. Yield: 2.1 grams (56.8%). Infrared confirmed the expected title composition.

The following is a table of compounds which are prepared according to the aforementioned procedures. Compound numbers have been assigned to them and are used for identification throughout the balance of the specification.

                                      TABLE I                                      __________________________________________________________________________      ##STR8##                                                                      Compound                                              m.p. °C. or       Number CMAB   X        Y    Z   R.sub.1  R.sub.2      n.sub.D.sup.30           __________________________________________________________________________     1      CHCl.sub.2                                                                            3-CF.sub.3                                                                              H    H   CH.sub.2 CHCH.sub.2                                                                     CH.sub.2 CHCH.sub.2                                                                         1.5002                   2      CHCl.sub.2                                                                            3-CF.sub.3                                                                              H    H   H        t-C.sub.4 H.sub.9                                                                           1.4754                   3      CHCl.sub.2                                                                            3-CF.sub.3                                                                              H    H                                                                                   ##STR9##             1.4990                   4      CHCl.sub.2                                                                            3-CF.sub.3                                                                              H    H   H                                                                                        ##STR10##   1.5083                   5      CHCl.sub.2                                                                            3-CF.sub.3                                                                              H    H   H        C.sub.3 H.sub.7                                                                             1.4810                   6      CHCl.sub.2                                                                            3-CF.sub.3                                                                              H    H   H        C.sub.4 H.sub.9                                                                             1.4833                   7      CHCl.sub.2                                                                            3-CF.sub.3                                                                              H    H   H                                                                                        ##STR11##   1.5310                   8      CHCl.sub.2                                                                            3-CF.sub.3                                                                              H    H   H                                                                                        ##STR12##   1.5650                   9      CHCl.sub.2                                                                            3-CF.sub.3                                                                              H    H   H        C.sub.6 H.sub.13                                                                            1.4823                   10     CHCl.sub.2                                                                            3-CF.sub.3                                                                              H    H   H        C.sub.2 H.sub.4 OH                                                                          1.5021                   11     CHCl.sub.2                                                                            3-CF.sub.3                                                                              H    H   H                                                                                        ##STR13##   Glass                    12     CHCl.sub.2                                                                            3-CF.sub.3                                                                              H    H   H        C.sub.5 H.sub.11                                                                            1.4800                   13     CHCl.sub.2                                                                            3-CF.sub.3                                                                              H    H   H        i-C.sub.4 H.sub.9                                                                           1.4760                   14     CHCl.sub.2                                                                            3-CF.sub.3                                                                              H    H   H        i-C.sub.4 H.sub.9                                                                           1.4770                   15     CHCl.sub.2                                                                            3-CF.sub.3                                                                              H    H   H        i-C.sub.3 H.sub.7                                                                           1.4770                   16     CHCl.sub.2                                                                            3-CF.sub.3                                                                              H    H   C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                             1.4890                   17     CHCl.sub.2                                                                            3-CF.sub.3                                                                              H    H   H        CH.sub.2 CHCH.sub.2                                                                         1.4986                   18     CHCl.sub.2                                                                            3-CF.sub.3                                                                              H    H   H        C.sub.2 H.sub.5                                                                             1.4873                   19     CHCl.sub.2                                                                            3-CF.sub.3                                                                              H    H                                                                                   ##STR14##            1.5140                   20     CHCl.sub.2                                                                            3-CF.sub.3                                                                              H    H                                                                                   ##STR15##            1.5184                   21     CHCl.sub.2                                                                            3-CF.sub.3                                                                              H    H                                                                                   ##STR16##            1.4818                   22     CHCl.sub.2                                                                            3-CF.sub.3                                                                              H    H                                                                                   ##STR17##            1.4948                   23     CHCl.sub.2                                                                            3-CF.sub.3                                                                              H    H   H                                                                                        ##STR18##   1.4678                   24     CH.sub.2 Cl                                                                           3-CF.sub.3                                                                              H    H   H        C.sub.3 H.sub.7                                                                             1.4810                   25     CH.sub.2 Cl                                                                           2-C.sub.2 H.sub.5                                                                       6-C.sub.2 H.sub.5                                                                   H   H        C.sub.3 H.sub.7                                                                             1.5100                   26     CH.sub.2 Cl                                                                           2-C.sub.2 H.sub.5                                                                       6-C.sub.2 H.sub.5                                                                   H   H        i-C.sub.3 H.sub.7                                                                           1.5212                   27     CH.sub.2 Cl                                                                           2-C.sub.2 H.sub.5                                                                       6-C.sub.2 H.sub.5                                                                   H   H        C.sub.4 H.sub.9                                                                             1.5103                   28     CH.sub.2 Cl                                                                           2-C.sub.2 H.sub.5                                                                       6-C.sub.2 H.sub.5                                                                   H   H        i-C.sub.4 H.sub.9                                                                           1.5090                   29     CH.sub.2 Cl                                                                           2-C.sub.2 H.sub.5                                                                       6-C.sub.2 H.sub.5                                                                   H   H        s-C.sub.4 H.sub.9                                                                           1.5021                   30     CH.sub.2 Cl                                                                           2-C.sub.2 H.sub.5                                                                       6-C.sub.2 H.sub.5                                                                   H   C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                             1.5150                   31     CH.sub.2 Cl                                                                           2-C.sub.2 H.sub.5                                                                       6-C.sub.2 H.sub.5                                                                   H   H        CH.sub.2 CHCH.sub.2                                                                         1.5230                   32     CH.sub.2 Cl                                                                           2-C.sub.2 H.sub.5                                                                       6-C.sub.2 H.sub.5                                                                   H   H        C.sub.5 H.sub.11                                                                            1.5032                   33     CH.sub.2 Cl                                                                           2-C.sub.2 H.sub.5                                                                       6-C.sub.2 H.sub.5                                                                   H   H         C(CH.sub.3).sub.2 CCH                                                                      1.5160                   34     CH.sub.2 Cl                                                                           2-C.sub.2 H.sub.5                                                                       6-C.sub.2 H.sub.5                                                                   H                                                                                   ##STR19##            1.5322                   35     CH.sub.2 Cl                                                                           2-C.sub.2 H.sub.5                                                                       6-C.sub.2 H.sub.5                                                                   H   C.sub.3 H.sub.7                                                                         C.sub.3 H.sub.7                                                                             1.5010                   36     CH.sub.2 Cl                                                                           2-C.sub.2 H.sub.5                                                                       6-C.sub.2 H.sub.5                                                                   H   H        CH(CH.sub.3)CH.sub.2 (CH.sub.3).s                                              ub.2         1.4900                   37     CH.sub.2 Cl                                                                           2-C.sub.2 H.sub.5                                                                       6-C.sub.2 H.sub.5                                                                   H   CH.sub.2 CHCH.sub.2                                                                     CH.sub.2 CHCH.sub.2                                                                         1.5180                   38     CH.sub.2 Cl                                                                           2-C.sub.2 H.sub.5                                                                       6-C.sub.2 H.sub.5                                                                   H                                                                                   ##STR20##            1.5323                   39     CH.sub.2 Cl                                                                           2-C.sub. 2 H.sub.5                                                                      6-C.sub.2 H.sub.5                                                                   H   H                                                                                        ##STR21##   1.5308                   40     CH.sub.2 Cl                                                                           2-C.sub.2 H.sub.5                                                                       6-C.sub.2 H.sub.5                                                                   H   H        CH.sub.2 CH(OCH.sub.3).sub.2                                                                1.5018                   41     CH.sub.2 Cl                                                                           2-C.sub.2 H.sub.5                                                                       6-C.sub.2 H.sub.5                                                                   H   CH.sub.3 OCH.sub.3    1.5110                   42     CH.sub.2 Cl                                                                           2-C.sub.2 H.sub.5                                                                       6-C.sub.2 H.sub.5                                                                   H   H        CH.sub.2 CN  Glass                    43     CHCl.sub.2                                                                            3-CF.sub.3                                                                              4-Cl H   H        C.sub.2 H.sub.5                                                                             1.5133                   44     CHCl.sub.2                                                                            3-CF.sub.3                                                                              4-Cl H   H        C.sub.3 H.sub.7                                                                             1.5073                   45     CHCl.sub.2                                                                            3-CF.sub.3                                                                              4-Cl H   H        i-C.sub.3 H.sub.7                                                                           1.5035                   46     CHCl.sub.2                                                                            3-CF.sub.3                                                                              4-Cl H   H        CH.sub.2 CHCH.sub.2                                                                         1.5181                   47     CHCl.sub.2                                                                            3-CF.sub.3                                                                              4-Cl H   H        c-C.sub.3 H.sub.5                                                                           1.5226                   48     CHCl.sub.2                                                                            3-CF.sub.3                                                                              4-Cl H   H        C.sub.4 H.sub.9                                                                             1.5058                   49     CHCl.sub. 2                                                                           3-CF.sub.3                                                                              4-Cl H   H        i-C.sub.4 H.sub.9                                                                           1.4980                   50     CHCl.sub.2                                                                            3-CF.sub.3                                                                              4-Cl H   H        s-C.sub.4 H.sub.9                                                                           1.4963                   51     CHCl.sub.2                                                                            3-CF.sub.3                                                                              4-Cl H   H        t-C.sub.4 H.sub.9                                                                           1.4923                   52     CHCl.sub.2                                                                            3-CF.sub.3                                                                              4-Cl H   C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                             1.5172                   53     CHCl.sub.2                                                                            3-CF.sub.3                                                                              4-Cl H   H        (CH.sub.2).sub.2 OCH.sub.3                                                                  1.5060                   54     CHCl.sub.2                                                                            3-CF.sub.3                                                                              4-Cl H   H        SC.sub.2 H.sub.5                                                                            1.5268                   55     CCl.sub.2 CH.sub.3                                                                    3-CF.sub.3                                                                              H    H   H        C.sub.3 H.sub.7                                                                             1.4768                   56     CCl.sub.2 CH.sub.3                                                                    3-CF.sub.3                                                                              H    H   H        C.sub.4 H.sub.9                                                                             1.4700                   57     CHCl.sub.2                                                                            3-CF.sub.3                                                                              H    H   H        c-C.sub.3 H.sub.5                                                                           1.4960                   58     CHCl.sub.2                                                                            3-CF.sub.3                                                                              H    H   H        CH.sub.2).sub.2 OCH.sub.3                                                                   1.4840                   59     CHCl.sub.2                                                                            3-CF.sub.3                                                                              H    H   H        C(CH.sub.3).sub.2 C.sub.2                                                      H.sub.5      1.4733                   60     CHCl.sub.2                                                                            3-CF.sub.3                                                                              H    H   H        CH.sub.2 CH(OCH.sub.3).sub.2                                                                1.4764                   61     CHCl.sub.2                                                                            3-CF.sub.3                                                                              5-CF.sub.3                                                                          H   H        i-C.sub.3 H.sub.7                                                                           1.4382                   62     CHCl.sub.2                                                                            4-Cl     H    H   H        i-C.sub.3 H.sub.7                                                                           1.4222                   63     CHCl.sub.2                                                                            3-CF.sub.3                                                                              5-CF.sub.3                                                                          H   H        C.sub.2 H.sub.5                                                                             1.4498                   64     CHCl.sub.2                                                                            3-CF.sub.3                                                                              5-CF.sub.3                                                                          H   H        C.sub.3 H.sub.7                                                                             1.4487                   65     CHCl.sub.2                                                                            3-CF.sub.3                                                                              5-CF.sub.3                                                                          H   H        CH.sub.2 CHCH.sub.2                                                                         1.4580                   66     CHCl.sub.2                                                                            3-CF.sub.3                                                                              5-CF.sub.3                                                                          H   H        c-C.sub.3 H.sub.5                                                                           1.4600                   67     CHCl.sub.2                                                                            3-CF.sub.3                                                                              5-CF.sub.3                                                                          H   H        C.sub.4 H.sub.9                                                                             1.4483                   68     CHCl.sub.2                                                                            3-CF.sub.3                                                                              5-CF.sub.3                                                                          H   H        i-C.sub.4 H.sub.9                                                                           1.4482                   69     CHCl.sub.2                                                                            3-CF.sub.3                                                                              5-CF.sub.3                                                                          H   H        s-C.sub.4 H.sub.9                                                                           1.4460                   70     CHCl.sub.2                                                                            3-CF.sub.3                                                                              5-CF.sub.3                                                                          H   H        (CH.sub.2).sub.2 OCH.sub.3                                                                  m.p. 68-71°                                                             C.                       71     CHCl.sub.2                                                                            3-CF.sub.3                                                                              5-CF.sub.3                                                                          H   H        (CH.sub.2 CH(OCH.sub.3).sub.2                                                               1.4490                   72     CHCl.sub.2                                                                            3-CF.sub.3                                                                              5-CF.sub.3                                                                          H   CH.sub.3 OCH.sub.3    1.4504                   73     CHCl.sub.2                                                                            3-CF.sub.3                                                                              5-CF.sub.3                                                                          H   C.sub. 2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                             1.4574                   74     CHCl.sub.2                                                                            3-NO.sub.2                                                                              5-CF.sub.3                                                                          H   H        C.sub.2 H.sub.5                                                                             1.5653                   75     CHCl.sub.2                                                                            3-NO.sub.2                                                                              5-CF.sub.3                                                                          H   H        i-C.sub.3 H.sub.7                                                                           1.5498                   76     CHCl.sub.2                                                                            3-NO.sub.2                                                                              5-CF.sub.3                                                                          H   H        C.sub.3 H.sub.7                                                                             1.5547                   77     CHCl.sub.2                                                                            3-NO.sub.2                                                                              5-CF.sub.3                                                                          H   H        CH.sub.2 CHCH.sub.2                                                                         1.5638                   78     CHCl.sub.2                                                                            3-NO.sub.2                                                                              5-CF.sub.3                                                                          H   H        i-C.sub.4 H.sub.9                                                                           1.5437                   79     CHCl.sub.2                                                                            3-NO.sub.2                                                                              5-CF.sub.3                                                                          H   H        s-C.sub.4 H.sub.9                                                                           1.5410                   80     CHCl.sub.2                                                                            3-NO.sub.2                                                                              5-CF.sub.3                                                                          H   H        (CH.sub.2).sub.2 OCH.sub.3                                                                  1.5540                   81     CHCl.sub.2                                                                            3-Cl     4-Cl H   H        C.sub.2 H.sub.5                                                                             1.5560                   82     CHCl.sub.2                                                                            3-Cl     4-Cl H   H        C.sub.3 H.sub.7                                                                             1.5575                   83     CHCl.sub.2                                                                            3-Cl     4-Cl H   H        i-C.sub.3 H.sub.7                                                                           m.p. 62-65°                                                             C.                       84     CHCl.sub.2                                                                            3-Cl     4-Cl H   H        CH.sub.2 CHCH.sub.2                                                                         1.5700                   85     CHCl.sub.2                                                                            3-CF.sub.3                                                                              H    H   H        N(CH.sub.3).sub.2                                                                           1.5198                   86     CHCl.sub.2                                                                            3-CF.sub.3                                                                              4-Cl H   H        CH.sub.3     1.5401                   87     CHCl.sub.2                                                                            3-Cl     4-Cl H   H        i-C.sub.4 H.sub.9                                                                           1.5643                   88     CHCl.sub.2                                                                            3-Cl     4-Cl H   H        s-C.sub.4 H.sub.9                                                                           1.5643                   89     CHCl.sub.2                                                                            3-Cl     4-Cl H   H        (CH.sub.2).sub.2 OCH.sub.3                                                                  1.5770                   90     CHCl.sub.2                                                                            3-Cl     4-Cl H   CH.sub.3 OCH.sub.3    1.5810                   91     CHCl.sub.2                                                                            3-Cl     5-Cl H   H        C.sub.2 H.sub.5                                                                             1.5818                   92     CHCl.sub.2                                                                            3-Cl     5-Cl H   H        C.sub.3 H.sub.7                                                                             1.5723                   93     CHCl.sub.2                                                                            3-Cl     5-Cl H   H        i-C.sub.3 H.sub.7                                                                           1.5653                   94     CHCl.sub.2                                                                            3-Cl     5-Cl H   H        CH.sub.2 CHCH.sub.2                                                                         1.5850                   95     CHCl.sub.2                                                                            3-Cl     5-Cl H   H        s-C.sub.4 H.sub.9                                                                           1.5613                   96     CHCl.sub.2                                                                            3-Cl     5-Cl H   H        CH.sub.2 CH.sub.2 OCH.sub.3                                                                 m.p. 67-70°                                                             C.                       97     CHCl.sub.2                                                                            3-Cl     5-Cl H   CH.sub.3 OCH.sub.3    1.5770                   98     CHCl.sub.2                                                                            3-Cl     H    H   H        C.sub.2 H.sub.5                                                                             1.5730                   99     CHCl.sub.2                                                                            3-Cl     H    H   H        C.sub. 3 H.sub.7                                                                            1.5669                   100    CHCl.sub.2                                                                            3-Cl     H    H   H        i-C.sub.3 H.sub.7                                                                           1.5620                   101    CHCl.sub.2                                                                            3-Cl     H    H   H        CH.sub.2 CHCH.sub.2                                                                         1.5831                   102    CHCl.sub.2                                                                            3-Cl     H    H   H        i-C.sub.4 H.sub.9                                                                           1.5578                   103    CHCl.sub.2                                                                            3-Cl     H    H   H        s-C.sub.4 H.sub.9                                                                           1.5555                   104    CHClCH.sub.3                                                                          3-CF.sub.3                                                                              H    H   H        C.sub.3 H.sub.7                                                                             1.4989                   105    CHClCH.sub.3                                                                          3-CF.sub.3                                                                              H    H   H        i-C.sub.3 H.sub.7                                                                           1.4904                   106    CHCl.sub.2                                                                            3-Cl     5-Cl H   H        i-C.sub.4 H.sub.9                                                                           1.5620                   107    CHCl.sub.2                                                                            3-CF.sub.3                                                                              H    H   H        CH(C.sub.2 H.sub.5)CH.sub.2                                                    OCH.sub.3    1.4974                   108    CHCl.sub.2                                                                            3-Cl     H    H   H        CH.sub.2 CH.sub.2 OCH.sub.3                                                                 1.4915                   109    CHCl.sub.2                                                                            3-Cl     H    H   CH.sub.3 OCH.sub.3    1.5700                   110    CHClCH.sub.3                                                                          3-CF.sub.3                                                                              H    H   H        CH.sub.2 CHCH                                                                               1.5057                   111    CHClCH.sub.3                                                                          3-CF.sub.3                                                                              H    H   H        i-C.sub.4 H.sub.9                                                                           1.4915                   112    CHClCH.sub.3                                                                          3-CF.sub.3                                                                              H    H   H        C.sub.4 H.sub.9                                                                             1.4893                   113    CHClCH.sub.3                                                                          3-CF.sub.3                                                                              H    H   H        (CH.sub.2).sub.2 OCH.sub.3                                                                  1.4957                   114    CHCl.sub.2                                                                            2-Cl     5-CF.sub.3                                                                          H   H        C.sub.2 H.sub.5                                                                             1.5170                   115    CHCl.sub.2                                                                            2-Cl     5-CF.sub.3                                                                          H   H        i-C.sub.3 H.sub.7                                                                           1.5090                   116    CHCl.sub.2                                                                            2-CF.sub.3                                                                              4-Cl H   H        C.sub.2 H.sub.5                                                                             1.5273                   117    CHCl.sub.2                                                                            2-CF.sub.3                                                                              4-Cl H   H        i-C.sub.3 H.sub.7                                                                           m.p. 80-82°                                                             C.                       118    CHCl.sub.2                                                                            3-NO.sub.2                                                                              4-Cl H   H        C.sub.2 H.sub.5                                                                             m.p. 82-84°                                                             C.                       119    CHCl.sub.2                                                                            3-NO.sub.2                                                                              4-Cl H   H        i-C.sub.3 H.sub.7                                                                           1.5810                   120    CHCl.sub.2                                                                            3-SCF.sub.3                                                                             H    H   H        C.sub.2 H.sub.5                                                                             1.5320                   121    CHCl.sub.2                                                                            3-SCF.sub.3                                                                             H    H   H        i-C.sub.3 H.sub.7                                                                           1.5810                   122    CHCl.sub.2                                                                             ##STR22##                                                                              H    H   H        i-C.sub.3 H.sub.7                                                                           Glassy solid             123    CHCl.sub.2                                                                            2-CF.sub.3                                                                              H    H   H        C.sub.2 H.sub.5                                                                             1.5140                   124    CHCl.sub.2                                                                            2-CF.sub.3                                                                              H    H   H        i-C.sub.3 H.sub.7                                                                           1.5054                   125    CHCl.sub.2                                                                            3-CH.sub.3                                                                              5-CH.sub.3                                                                          H   H        C.sub.2 H.sub.5                                                                             m.p. 75-78°                                                             C.                       126    CHCl.sub.2                                                                            3-CH.sub.3                                                                              5-CH.sub.3                                                                          H   H        i-C.sub.3 H.sub.7                                                                           1.5310                   127    CHCl.sub.2                                                                            2-Cl     3-Cl H   H        C.sub.2 H.sub.5                                                                             1.5823                   128    CHCl.sub.2                                                                            2-Cl     3-Cl H   H        i-C.sub.3 H.sub.7                                                                           1.5650                   129    CHCl.sub.2                                                                            2-Cl     4-Cl H   H        C.sub.2 H.sub.5                                                                             1.5790                   130    CHCl.sub.2                                                                            2-Cl     4-Cl H   H        i-C.sub.3 H.sub.7                                                                           1.5700                   131    CHCl.sub.2                                                                            2-Cl     6-Cl H   H        C.sub.2 H.sub.5                                                                             1.5728                   132    CHCl.sub.2                                                                            2-Cl     2-Cl H   H        i-C.sub.3 H.sub.7                                                                           1.5590                   133    CHCl.sub.2                                                                            3-CN     H    H   H        C.sub.2 H.sub.5                                                                             1.5673                   134    CHCl.sub.2                                                                            3-CN     H    H   H        i-C.sub.3 H.sub.7                                                                           1.5620                   135    CHCl.sub.2                                                                            2-CH.sub.3                                                                              6-CH.sub.3                                                                          H   H        C.sub.2 H.sub.5                                                                             1.5450                   136    CHCl.sub.2                                                                            2-C.sub.2 H.sub.5                                                                       6-C.sub.2 H.sub.5                                                                   H   H        C.sub.2 H.sub.5                                                                             1.5410                   137    CHCl.sub.2                                                                            3-NO.sub.2                                                                              5-NO.sub.2                                                                          H   H        C.sub.2 H.sub.5                                                                             m.p. 110-                                                                      112° C.           138    CHCl.sub.2                                                                            3-NO.sub.2                                                                              5-NO.sub.2                                                                          H   H        i-C.sub.3 H.sub.7                                                                           m.p.                                                                           132-134° C.       139    CHCl.sub.2                                                                            2-NO.sub.2                                                                              4-CF.sub.3                                                                          H   H        C.sub.2 H.sub.5                                                                             1.5180                   140    CHCl.sub.2                                                                            2-NO.sub.2                                                                              4-CF.sub.3                                                                          H   H        i-C.sub.3 H.sub.7                                                                           1.5240                   141    CHCl.sub.2                                                                            2-Cl     4-CH.sub.3                                                                          H   H        C.sub.2 H.sub.5                                                                             1.5421                   142    CHCl.sub.2                                                                            2-Cl     4-CH.sub.3                                                                          H   H        i-C.sub.3 H.sub.7                                                                           1.5428                   143    CHCl.sub.2                                                                            2-Cl     5-CH.sub.3                                                                          H   H        C.sub.2 H.sub.5                                                                             1.5568                   144    CHCl.sub.2                                                                            2-Cl     5-CH.sub.3                                                                          H   H        i-C.sub.3 H.sub.7                                                                           1.5412                   145    CHCl.sub.2                                                                            2-Cl     6-CH.sub.3                                                                          H   H        C.sub.2 H.sub.5                                                                             1.5510                   146    CHCl.sub.2                                                                            2-Cl     6-CH.sub.3                                                                          H   H        i-C.sub.3 H.sub.7                                                                           1.5390                   147    CHCl.sub.2                                                                            2-CH.sub.3                                                                              3-Cl H   H        C.sub.2 H.sub.5                                                                             1.5563                   148    CHCl.sub.2                                                                            2-CH.sub.3                                                                              3-Cl H   H        i-C.sub.3 H.sub.7                                                                           1.5440                   149    CHCl.sub.2                                                                            3-Cl     4-CH.sub.3                                                                          H   H        C.sub.2 H.sub.5                                                                             1.5600                   150    CHCl.sub.2                                                                            3-Cl     4-CH.sub.3                                                                          H   H         i-C.sub.3 H.sub.7                                                                          1.5610                   151    CHCl.sub.2                                                                            2-CH.sub.3                                                                              4-Cl H   H        C.sub.2 H.sub.5                                                                             1.5534                   152    CHCl.sub.2                                                                            2-CH.sub.3                                                                              4-Cl H   H        i-C.sub.3 H.sub.7                                                                           1.5438                   153    CHCl.sub.2                                                                            2-CH.sub.3                                                                              5-Cl H   H        C.sub.2 H.sub.5                                                                             1.5513                   154    CHCl.sub.2                                                                            2-CH.sub.3                                                                              5-Cl H   H        i-C.sub.3 H.sub.7                                                                           m.p. 90-93°                                                             C.                       155    CHCl.sub.2                                                                            2-CH.sub.3                                                                              H    H   H        i-C.sub.3 H.sub.7                                                                           1.5306                   156    CHCl.sub.2                                                                            2-Cl     5-Cl H   H        C.sub.2 H.sub.5                                                                             1.5610                   157    CHCl.sub.2                                                                            2-Cl     5-Cl H   H        i-C.sub.3 H.sub.7                                                                           1.5487                   158    CHCl.sub.2                                                                            3-CH.sub.3                                                                              H    H   H        C.sub.2 H.sub.5                                                                             1.5428                   159    CHCl.sub.2                                                                            3-CH.sub.3                                                                              H    H   H        i-C.sub.3 H.sub.7                                                                           1.5274                   160    CHCl.sub.2                                                                            2-CH.sub.3                                                                              3-CH.sub.3                                                                          H   H        C.sub.2 H.sub.5                                                                             1.5528                   161    CHCl.sub.2                                                                            2-CH.sub.3                                                                              3-CH.sub.3                                                                          H   H        i-C.sub.3 H.sub.7                                                                           1.5403                   162    CHCl.sub.2                                                                            3-CH.sub.3                                                                              4-CH.sub.3                                                                          H   H        C.sub.2 H.sub.5                                                                             1.5595                   163    CHCl.sub.2                                                                            3-CH.sub.3                                                                              4-CH.sub.3                                                                          H   H        i-C.sub.3 H.sub.7                                                                           1.5438                   164    CHCl.sub.2                                                                            2-CH.sub.3                                                                              5-CH.sub.3                                                                          H   H        C.sub.2 H.sub.5                                                                             1.5480                   165    CHCl.sub.2                                                                            2-CH.sub.3                                                                              5-CH.sub.3                                                                          H   H        i-C.sub.3 H.sub.7                                                                           1.5343                   166    CHCl.sub.2                                                                            2-OCH.sub.3                                                                             5-OCH.sub.3                                                                         H   H        C.sub.2 H.sub.5                                                                             1.5593                   167    CHCl.sub.2                                                                            2-OCH.sub.3                                                                             5-OCH.sub.3                                                                         H   H        i-C.sub.3 H.sub.7                                                                           1.5506                   168    CHCl.sub.2                                                                            2-Cl     4-Cl 6-Cl                                                                               H        C.sub.2 H.sub.5                                                                             m.p. 71-74°                                                             C.                       169    CHCl.sub.2                                                                            2-Cl     4-Cl 6-Cl                                                                               H        i-C.sub.3 H.sub.7                                                                           1.5743                   170    CHCl.sub.2                                                                            2-CH.sub.3                                                                              4-CH.sub.3                                                                          H   H        i-C.sub.3 H.sub.7                                                                           1.5473                   171    CHCl.sub.2                                                                            2-CH.sub.3                                                                              4-CH.sub.3                                                                          H   H        C.sub.2 H.sub.5                                                                             1.5473                   172    CHCl.sub.2                                                                            2-CH.sub.3                                                                              5-NO.sub.2                                                                          H   H        C.sub.2 H.sub.5                                                                             m.p. 96-100°                                                            C.                       173    CHCl.sub.2                                                                            2-OCH.sub.3                                                                             5-NO.sub.2                                                                          H   H        i-C.sub.3 H.sub.7                                                                           m.p. 74-78°                                                             C.                       174    CHCl.sub.2                                                                            3-C(O)CH.sub.3                                                                          H    H   H        i-C.sub.3 H.sub.7                                                                           1.5590                   175    CHCl.sub.2                                                                            2-Cl     H    H   H        i-C.sub.3 H.sub.7                                                                           1.5560                   176    CHCl.sub.2                                                                            3-Br     H    H   H        i-C.sub.3 H.sub.7                                                                           1.5688                   177    CHCl.sub.2                                                                            2-Br     H    H   H        i-C.sub.3 H.sub.7                                                                           1.5655                   178    CHCl.sub.2                                                                            4-Br     H    H   H        i-C.sub.3 H.sub.7                                                                           1.5679                   179    CHCl.sub.2                                                                            3-CH.sub.3 O                                                                            H    H   H        i-C.sub.3 H.sub.7                                                                           1.5463                   180    CHCl.sub.2                                                                             ##STR23##                                                                              H    H   H        i-C.sub.3 H.sub.7                                                                           1.5523                   181    CHCl.sub.2                                                                            3-CH.sub.3                                                                              5-CH.sub.3                                                                          H   CH(CH.sub.3).sub.2                                                                       ##STR24##   Dark oil                 182    CHClF  3-CH.sub.3                                                                              5-CH.sub.3                                                                          H   H        i-C.sub.3 H.sub.7                                                                           m.p. 37-40°                                                             C.                       183    CHClF  2-Cl     3-Cl H   H        i-C.sub.3 H.sub.7                                                                           Dark oil                 184    CHClF  3-Cl     5-Cl H   H        i-C.sub.3 H.sub.7                                                                           1.5540                   185    CHCl.sub.2                                                                            2-OCH.sub.3                                                                             4-OCH.sub.3                                                                         5-Cl                                                                               H        i-C.sub.3 H.sub.7                                                                           1.5545                   186    CHCl.sub.2                                                                            2-NO.sub.2                                                                              4-Cl H   H        i-C.sub.3 H.sub.7                                                                           1.5786                   187    CHCl.sub.2                                                                            3-NO.sub.2                                                                              4-Cl H   H        i-C.sub.3 H.sub.7                                                                           m.p. 83-86°                                                             C.                       188    CHCl.sub.2                                                                            3-NO.sub.2                                                                              6-Cl H   H        i-C.sub.3 H.sub.7                                                                           m.p. 60-63°                                                             C.                       189    CHCl.sub.2                                                                            2-Cl     4-NO.sub.2                                                                          H   H        i-C.sub.3 H.sub.7                                                                           m.p. 84-88°                                                             C.                       190    CHCl.sub.2                                                                            2-CH.sub.3                                                                              5-NO.sub.2                                                                          H   H        i-C.sub.3 H.sub.7                                                                           m.p. 54-58°                                                             C.                       191    CHCl.sub.2                                                                            2-NO.sub.2                                                                              4-CH.sub.3                                                                          H   H        i-C.sub.3 H.sub.7                                                                           1.5688                   192    CHCl.sub.2                                                                            3-NO.sub.2                                                                              4-CH.sub.3                                                                          H   H        i-C.sub.3 H.sub.7                                                                           1.5677                   193    CHCl.sub.2                                                                            2-F      H    H   H        i-C.sub.3 H.sub.7                                                                           1.5352                   194    CHCl.sub.2                                                                            2-OCH.sub.3                                                                             4-NO.sub.2                                                                          H   H        i-C.sub.3 H.sub.7                                                                           1.5980                   195    CHCl.sub.2                                                                            2-F      4-F  H   H        i-C.sub.3 H.sub.7                                                                           1.5173                   196    CHCl.sub.2                                                                            2-i-C.sub.3 H.sub.7                                                                     6-i-C.sub.3 H.sub.7                                                                 H   H        i-C.sub.3 H.sub.7                                                                           m.p. 80-82°                                                             C.                       197    CHCl.sub.2                                                                            3-NO.sub.2                                                                              4-F  H   H        i-C.sub.3 H.sub.7                                                                           m.p.                                                                           88.5-91° C.       198    CHCl.sub.2                                                                            3-Cl     5-Cl H   H        c-C.sub.3 H.sub.7                                                                           Low melting                                                                    solid                    199    CHCl.sub.2                                                                            2-Cl     3-Cl H   CH.sub.2 CHCH.sub.2                                                                     CH.sub.2 CHCH.sub.2                                                                         1.5860                   200    CHCl.sub.2                                                                            3-CH.sub.3                                                                              5-CH.sub.3                                                                          H   CH.sub.2 CHCH.sub.2                                                                     CH.sub.2 CHCH.sub.2                                                                         1.5610                   201    CHCl.sub.2                                                                            2-CH.sub.3                                                                              3-Cl H   CH.sub.2 CHCH.sub.2                                                                     CH.sub.2 CHCH.sub.2                                                                         1.5744                   202    CHCl.sub.2                                                                            2-CH.sub.3                                                                              3-Cl H   CH.sub.2 CHCH.sub.2                                                                     CH.sub.2 CHCH.sub.2                                                                         1.5787                   203    CHCl.sub.2                                                                            2-Cl     3-Cl H   H        CH.sub.2 CHCH.sub.2                                                                         1.5924                   204    CHCl.sub.2                                                                            3-CH.sub.3                                                                              5-CH.sub.3                                                                          H   H        CH.sub.2 CHCH.sub.2                                                                         1.5629                   205    CHCl.sub.2                                                                            2-CH.sub.3                                                                              3-Cl H   H        n-C.sub.3 H.sub.7                                                                           1.5648                   206    CHCl.sub.2                                                                            2-Cl     3-Cl H   H        n-C.sub.3 H.sub.7                                                                           1.5784                   207    CHCl.sub.2                                                                            3-CH.sub.3                                                                              5-CH.sub.3                                                                          H   H        n-C.sub.3 H.sub.7                                                                           1.5505                   208    CHBrF  3-Cl     5-Cl H   H        i-C.sub.3 H.sub.7                                                                           Dark oil                 209    CHCl.sub.2                                                                            2-Cl     5-Cl H   H        CH.sub.2 CHCH.sub.2                                                                         1.5897                   210    CHF.sub. 2                                                                            3-Cl     5-Cl H   H        i-C.sub.3 H.sub.7                                                                           1.5425                   211    CHCl.sub.2                                                                            2-Cl     4-Cl 5-Cl                                                                               CH.sub.3 CH.sub.3     1.5882                   __________________________________________________________________________

                                      TABLE I-A                                    __________________________________________________________________________      ##STR25##                                                                     Compound                                                                       Number                                                                              CMAB  X    Y    Z  R.sub.1                                                                          R.sub.2  Acid Salt       m.p. °C. or                                                             n.sub.D.sup.30              __________________________________________________________________________     212  CHCl.sub.2                                                                           3-CF.sub.3                                                                          H    H  H i-C.sub.4 H.sub.9                                                                       HCl             m.p. 127-128°                                                           C.                          213  CHCl.sub.2                                                                           3-CF.sub.3                                                                          4-Cl H  H C.sub.3 H.sub.7                                                                         HCl             m.p. 139-141°                                                           C.                          214  CHCl.sub.2                                                                           3-CF.sub.3                                                                          4-Cl H  H i-C.sub.3 H.sub.7                                                                       HCl             m.p. 169-172°                                                           C.                          215  CHCl.sub.2                                                                           3-CF.sub.3                                                                          4-Cl H  H CH.sub.2 CHCH.sub.2                                                                     HCl             m.p. 115-120°                                                           C.                          216  CHCl.sub.2                                                                           3-CF.sub.3                                                                          4-Cl H  H i-C.sub.3 H.sub.7                                                                       CCl.sub.3 COOH  1.4863                      217  CHCl.sub.2                                                                           3-CF.sub.3                                                                          H    H  H  i-C.sub.3 H.sub.7                                                                      HCl             m.p. 191-194°                                                           C.                          218  CHCl.sub.2                                                                           3-CF.sub.3                                                                          5-CF.sub.3                                                                          H  H C.sub.2 H.sub.5                                                                         HCl             m.p. 195-197°                                                           C.                          219  CHCl.sub.2                                                                           3-NO.sub.2                                                                          H    H  H i-C.sub.3 H.sub.7                                                                       HCl             m.p. 165-167°                                                           C.                          220  CHCl.sub.2                                                                           3-Cl 4-Cl H  H i-C.sub.3 H.sub.7                                                                       HCl             m.p. 202-204°                                                           C.                          221  CHCl.sub.2                                                                           3-Cl 5-Cl H  H i-C.sub.3 H.sub.7                                                                       HCl             m.p. 198-202°                                                           C.                          222  CHCl.sub.2                                                                           2-Cl 5-CF.sub.3                                                                          H  H C.sub.2 H.sub.5                                                                         HCl             m.p. 185-188°                                                           C.                          223  CHCl.sub.2                                                                           2-Cl 5-CF.sub.3                                                                          H  H i-C.sub.3 H.sub.7                                                                       HCl             m.p. 178-179°                                                           C.                          224  CHCl.sub.2                                                                           2-CF.sub.3                                                                          4-Cl H  H C.sub.2 H.sub.5                                                                         HCl             m.p. 149-150°                                                           C.                          225  CHCl.sub.2                                                                           2-CF.sub.3                                                                          4-Cl H  H i-C.sub.3 H.sub.7                                                                       HCl             (Foam)                      226  CHCl.sub.2                                                                           3-NO.sub.2                                                                          4-Cl H  H C.sub.2 H.sub.5                                                                         HCl             m.p. 148-150°                                                           C.                          227  CHCl.sub.2                                                                           3-NO.sub.2                                                                          4-Cl H  H i-C.sub.3 H.sub.7                                                                       HCl             m.p. 137-140°                                                           C.                          228  CHCl.sub.2                                                                           3-SCF.sub.3                                                                         H    H  H C.sub.2 H.sub.5                                                                         HCl             m.p. 136-138°                                                           C.                          229  CHCl.sub.2                                                                           3-SCF.sub.3                                                                         H    H  H i-C.sub.3 H.sub.7                                                                       HCl             m.p. 147-150°                                                           C.                          230  CHCl.sub.2                                                                           2-CF.sub.3                                                                          H    H  H C.sub.2 H.sub.5                                                                         HCl             1.5140                      231  CHCl.sub.2                                                                           2-CF.sub.3                                                                          H    H  H i-C.sub.3 H.sub.7                                                                       HCl             m.p. 159-161°                                                           C.                          232  CHCl.sub.2                                                                           3-CH.sub.3                                                                          5-CH.sub.3                                                                          H  H C.sub.2 H.sub.5                                                                         HCl             m.p. 152-154°                                                           C.                          233  CHCl.sub.2                                                                           3-CH.sub.3                                                                          5-CH.sub.3                                                                          H  H i-C.sub.3 H.sub.7                                                                       HCl             m.p. 194-197°                                                           C.                          234  CHCl.sub.2                                                                           2-Cl 3-Cl H  H C.sub.2 H.sub.5                                                                         HCl             m.p. 176-180°                                                           C.                          235  CHCl.sub.2                                                                           2-Cl 3-Cl H  H i-C.sub.3 H.sub.7                                                                       HCl             m.p. 199-203°                                                           C.                          236  CHCl.sub.2                                                                           2-Cl 4-Cl H  H C.sub.2 H.sub.5                                                                         HCl             m.p. 125-129°                                                           C.                          237  CHCl.sub.2                                                                           2-Cl 4-Cl H  H i-C.sub.3 H.sub.7                                                                       HCl             m.p. 159-161°                                                           C.                          238  CHCl.sub.2                                                                           2-Cl 6-Cl H  H C.sub.2 H.sub.5                                                                         HCl             m.p. 177-181°                                                           C.                          239  CHCl.sub.2                                                                           2-Cl 6-Cl H  H i-C.sub.3 H.sub.7                                                                       HCl             m.p. 195-198°                                                           C.                          240  CHCl.sub.2                                                                           3-CN H    H  H C.sub.2 H.sub.5                                                                         HCl             m.p. 136-140°                                                           C.                          241  CHCl.sub.2                                                                           3-CN H    H  H i-C.sub.3 H.sub.7                                                                       HCl             m.p. 167-169°                                                           C.                          242  CHCl.sub.2                                                                           2-CH.sub.3                                                                          6-CH.sub.3                                                                          H  H C.sub.2 H.sub.5                                                                         HCl             m.p. 183-186°                                                           C.                          243  CHCl.sub.2                                                                           2-CH.sub.3                                                                          6-CH.sub.3                                                                          H  H i-C.sub.3 H.sub.7                                                                       HCl             m.p. 198-202°                                                           C.                          244  CHCl.sub.2                                                                           2-C.sub.2 H.sub.5                                                                   6-C.sub.2 H.sub.5                                                                   H  H C.sub.2 H.sub.5                                                                         HCl             m.p. 175-179°                                                           C.                          245  CHCl.sub.2                                                                           2-C.sub.2 H.sub.5                                                                   6-C.sub.2 H.sub.5                                                                   H  H i-C.sub.3 H.sub.7                                                                       HCl             m.p. 195-198°                                                           C.                          246  CHCl.sub.2                                                                           3-NO.sub.2                                                                          5-NO.sub.2                                                                          H  H C.sub.2 H.sub.5                                                                         HCl             m.p. 201-202°                                                           C.                          247  CHCl.sub.2                                                                           3-NO.sub.2                                                                          5-NO.sub.2                                                                          H  H i-C.sub. 3 H.sub.7                                                                      HCl             m.p. 197-202°                                                           C.                          248  CHCl.sub.2                                                                           2-NO.sub.2                                                                          4-CF.sub.3                                                                          H  H C.sub.2 H.sub.5                                                                         HCl             Glass                       249  CHCl.sub.2                                                                           2-NO.sub.2                                                                          4-CF.sub.3                                                                          H  H i-C.sub.3 H.sub.7                                                                       HCl             m.p. 152-155°                                                           C.                          250  CHCl.sub.2                                                                           2-Cl 4-CH.sub.3                                                                          H  H C.sub.2 H.sub.5                                                                         HCl             m.p. 160-163°                                                           C.                          251  CHCl.sub.2                                                                           2-Cl 4-CH.sub.3                                                                          H  H i-C.sub.3 H.sub.7                                                                       HCl             m.p. 183-184°                                                           C.                          252  CHCl.sub.2                                                                           2-Cl 5-CH.sub.3                                                                          H  H C.sub.2 H.sub.5                                                                         HCl             m.p. 184-185°                                                           C.                          253  CHCl.sub.2                                                                           2-Cl 5-CH.sub.3                                                                          H  H i-C.sub.3 H.sub.7                                                                       HCl             m.p. 206-207°                                                           C.                          254  CHCl.sub.2                                                                           2-Cl 6-CH.sub.3                                                                          H  H C.sub.2 H.sub.5                                                                         HCl             m.p. 166-168°                                                           C.                          255  CHCl.sub.2                                                                           2-Cl 6-CH.sub.3                                                                          H  H i-C.sub.3 H.sub.7                                                                       HCl             m.p. 185-187°                                                           C.                          256  CHCl.sub.2                                                                           2-CH.sub.3                                                                          3-Cl H  H C.sub.2 H.sub.5                                                                         HCl             m.p. 188-191°                                                           C.                          257  CHCl.sub.2                                                                           2-CH.sub.3                                                                          3-Cl H  H i-C.sub.3 H.sub. 7                                                                      HCl             m.p. 236° C.                                                            dec.                        258  CHCl.sub.2                                                                           3-Cl 4-CH.sub.3                                                                          H  H C.sub.2 H.sub.5                                                                         HCl             m.p. 166-169°                                                           C.                          259  CHCl.sub.2                                                                           3-Cl 4-CH.sub.3                                                                          H  H i-C.sub.3 H.sub.7                                                                       HCl             m.p. 183-186°                                                           C.                          260  CHCl.sub.2                                                                           2-CH.sub.3                                                                          4-Cl H  H C.sub.2 H.sub.5                                                                         HCl             m.p. 184-186°                                                           C.                          261  CHCl.sub.2                                                                           2-CH.sub.3                                                                          4-Cl H  H i-C.sub.3 H.sub.7                                                                       HCl             m.p. 193-195°                                                           C.                          262  CHCl.sub.2                                                                           2-CH.sub.3                                                                          5-Cl H  H C.sub.2 H.sub.5                                                                         HCl             m.p. 165-166°                                                           C.                          263  CHCl.sub.2                                                                           2-CH.sub.3                                                                          5-Cl H  H i-C.sub.3 H.sub.7                                                                       HCl             m.p. 211-213°                                                           C.                          264  CHCl.sub.2                                                                           2-CH.sub.3                                                                          H    H  H i-C.sub.3 H.sub.7                                                                       HCl             m.p. 223-224°                                                           C. dec.                     265  CHCl.sub.2                                                                           3-CF.sub.3                                                                          5-CF.sub.3                                                                          H  H i-C.sub.3 H.sub.7                                                                       HCl             m.p. 158-160°                                                           C.                          266  CHCl.sub.2                                                                           2-Cl 5-Cl H  H C.sub.2 H.sub.5                                                                         HCl             m.p. 183-184°                                                           C.                          267  CHCl.sub.2                                                                           2-Cl 5-Cl H  H i-C.sub.3 H.sub. 7                                                                      HCl             m.p. 196-199°                                                           C.                          268  CHCl.sub.2                                                                           3-CH.sub.3                                                                          H    H  H C.sub.2 H.sub.5                                                                         HCl             m.p. 134-136°                                                           C.                          269  CHCl.sub.2                                                                           3-CH.sub.3                                                                          H    H  H i-C.sub.3 H.sub.7                                                                       HCl             m.p. 212-215°                                                           C.                          270  CHCl.sub.2                                                                           2-CH.sub.3                                                                          3-CH.sub.3                                                                          H  H C.sub.2 H.sub.5                                                                         HCl             m.p. 187-189°                                                           C.                          271  CHCl.sub.2                                                                           2-CH.sub.3                                                                          3-CH.sub.3                                                                          H  H i-C.sub.3 H.sub.7                                                                       HCl             m.p. 243-244°                                                           C.                          272  CHCl.sub.2                                                                           3-CH.sub.3                                                                          4-CH.sub.3                                                                          H  H C.sub.2 H.sub.5                                                                         HCl             m.p. 140-142°                                                           C.                          273  CHCl.sub.2                                                                           3-CH.sub.3                                                                          4-CH.sub.3                                                                          H  H i-C.sub.3 H.sub.7                                                                       HCl             m.p. 213-219°                                                           C.                          274  CHCl.sub.2                                                                           2-CH.sub.3                                                                          5-CH.sub.3                                                                          H  H C.sub.2 H.sub.5                                                                         HCl             m.p. 134-137°                                                           C.                          275  CHCl.sub.2                                                                           2-CH.sub.3                                                                          5-CH.sub.3                                                                          H  H i-C.sub.3 H.sub.7                                                                       HCl             m.p. 230-231°                                                           C.                          276  CHCl.sub.2                                                                           2-OCH.sub.3                                                                         5-OCH.sub.3                                                                         H  H C.sub.2 H.sub.5                                                                         HCl             m.p. 146-149°                                                           C.                          277  CHCl.sub.2                                                                           2-Cl 4-Cl 6-Cl                                                                              H C.sub.2 H.sub.5                                                                         HCl             m.p. 194° C.                                                            dec.                        278  CHCl.sub.2                                                                           2-Cl 4-Cl 6-Cl                                                                              H i-C.sub.3 H.sub.7                                                                       HCl             m.p. 188° C.                                                            dec.                        279  CHCl.sub.2                                                                           2-CH.sub.3                                                                          4-CH.sub.3                                                                          H  H i-C.sub.3 H.sub.7                                                                       HCl             m.p. 186-188°                                                           C.                          280  CHCl.sub.2                                                                           2-CH.sub.3                                                                          4-CH.sub.3                                                                          H  H C.sub.2 H.sub.5                                                                         HCl             m.p. 161-165°                                                           C.                          281  CHCl.sub.2                                                                           2-CH.sub.3                                                                          5-NO.sub.2                                                                          H  H C.sub.2 H.sub.5                                                                         HCl             m.p. 165-168°                                                           C.                          282  CHCl.sub.2                                                                           2-OCH.sub.3                                                                         5-NO.sub.2                                                                          H  H i-C.sub.3 H.sub.7                                                                       HCl             m.p. 129-131°                                                           C. dec.                     283  CHCl.sub.2                                                                           3-CH.sub.3                                                                          5-CH.sub.3                                                                          H  H i-C.sub.3 H.sub.7                                                                       2,4-dichloro phenoxy acetic                                                                    Very viscous oil            284  CHCl.sub.2                                                                           3-CH.sub.3                                                                          5-CH.sub.3                                                                          H  H i-C.sub.3 H.sub.7                                                                       Dichloro benzoic acid                                                                          Semi-solid                  285  CHCl.sub.2                                                                           3-Cl 5-Cl H  H i-C.sub.3 H.sub.7                                                                       Hexanoic acid salt                                                                             1.5150                      286  CHCl.sub.2                                                                           3-Cl 5-Cl H  H i-C.sub.3 H.sub.7                                                                       Naphthalene acetic acid                                                                        m.p. 131° C.         287  CHCl.sub.2                                                                           3-Cl 5-Cl H  H i-C.sub.3 H.sub.7                                                                       Trifluoroacetic acid                                                                           Semi-solid                  288  CHCl.sub.2                                                                           3-Cl 5-Cl H  H i-C.sub.3 H.sub.7                                                                       Pivalic acid    n.sub.D.sup.30 1.5192       289  CHCl.sub.2                                                                           3-Cl 5-Cl H  H i-C.sub.3 H.sub.7                                                                       Stearic acid    Semi-solid                  290  CHCl.sub.2                                                                           3-Cl 5-Cl H  H i-C.sub.3 H.sub.7                                                                       10-undecenoic acid                                                                             n.sub.D.sup.30 1.5163       291  CHCl.sub.2                                                                           3-Cl 5-Cl H  H i-C.sub.3 H.sub.7                                                                       Benzoic acid    Semi-solid                  292  CHCl.sub.2                                                                           3-Cl 5-Cl H  H i-C.sub.3 H.sub.7                                                                       Melonic acid    Semi-solid                  293  CHCl.sub.2                                                                           3-Cl 5-Cl H  H i-C.sub.3 H.sub.7                                                                       Succinic acid   Semi-solid                  294  CHCl.sub.2                                                                           3-Cl 5-Cl H  H i-C.sub.3 H.sub.7                                                                       Maleic acid     n.sub.D.sup.30              __________________________________________________________________________                                                        1.5523                 

HERBICIDE SCREENING TESTS

As previously mentioned, the herein described compounds produced in the above-described manner are phytotoxic compounds which are useful and valuable in conrolling various plant species. Compounds of this invention were tested as herbicides in the following manner.

A. Pre-emergence Herbicide Screening Test

Using an analytical balance, 300 milligrams of the compound to be tested is weighed on a piece of glassine weighing paper. The paper and compound are placed in a 2 oz. amber bottle and dissolve in 45 milliliters of acetone. If the material is not soluble in acetone, another solvent such as water, alcohol, or dimethylformamide (DMF) is used. When DMF is used, only 1.5 milliliters o less are used to dissolve the compound and then another solvent is used to bring the volume to 45 milliliters. Twenty milliliters of this solution is transferred to a 80 milliliter wide-mouth amber bottle and diluted with 24.5 milliliters of a water and acetone mixture (10:1) containing 1% Tween 20® (polyoxyethylene sorbitan monolaurate). The solution is sprayed on the seeded flat on a linear spray table calibrated to deliver 80 gallon per acre, the application rate is 2 lb/acre (2.24 kg/hectare).

When applied at 8 lb/acre (8.96 kg/hectare), 20 milligrams of the compound to be tested are weighed onto a glassine weighing paper, placed into a 30 milliliter vial, and dissolved in 3 milliliters acetone containing 1% Tween 20® . If the material is not soluble in acetone, another solvent such as water, alcohol, or dimethylformamide (DMF) is used. When DMF is used, only 0.5 milliliters or less are used to dissolve the compound and then another solvent is used to bring the volume to 3 milliliters. The solution is atomized onto the seeded flat using a No. 152 DeVilbiss atomizer at a pressure of 5 lb/square inch (0.35 kg/cm²), and the spray volume was 143 gallons per acre (1338 liter per hectare).

On the day preceeding treatment, a flat is filled with sandy loam soil fortified with 50 ppm 17-17-17 fertilizer and Captan®. Seven rows are impressed across the width of the flat and seeded with one species per row. The seeds are covered with soil so that they are planted at a depth of 1.2 centimeters. The species are hairy crabgrass (CG) (Digitaria sanguinalis), foxtail (FT) (Setaria spp.), watergrass (WG) (Echinochloa crusgali), wild oat (WO) (Avena fatua), mustard (MD) (Brassica juncea), curly dock (CD) (Rumex crispus), and pigweed (PW) (Amaranthus retroflexus) is seeded between the last row and the end of the flat at a depth of 1 centimeter. Ample seeds are planted to give about 20 to 50 seedlings per row after emergence depending on the size of the plant at the time of rating. At the 8 lb/acre testing rate red oat (RO) (Avena sativa) is used instead of wild oat.

After treatment, the flats are placed in the greenhouse at a temperature of 70° to 85° F. and water by sprinkling. Two weeks after treatment the degree of injury or control is determined by comparison with untreated plants of the same age. The injury rating is recorded as 0 to 100% for each species where 0 represents no injury and 100% represents complete kill.

B. Post-emergence Herbicide Screening Test

The procedure for this test is substantially the same as the pre-emergence herbicide screening test A. The seeds of the plant species for the 2 lb/acre test are described in screening test A. The seeds for the 8 lb/acre post-emergence test included: hairy crabgrass, watergrass, red oat, mustard, curly dock and pinto beans (BN) (Phaseolus vulgaris). The flats are seeded and placed in the greenhouse 8-12 days prior to treatment with the candidate compounds. The plant foliage was sprayed with solutions of the candidate compounds.

For the 8 lb/acre solution, 20 milligrams of the test compound was weighed out and dissolved as described above except that 2.5 milliliters acetone with 1% Tween 20® or other suitable solvent plus 2.5 milligrams of water was atomized as described above. The spray volume as 238 gallons per acre (2226 liters per hectare). The rate at 2 lb/acre (2.24 kg/hectare) was achieved using the linear spray table as described above.

The results of these tests are shown in Table II.

                                      TABLE II                                     __________________________________________________________________________     Herbicidal Activity - Screening Results                                        __________________________________________________________________________     Percent Control at 8 lb/A                                                      Compound                                                                             Pre-emergence        Post-emergence                                      Number                                                                               CG FT WG RO PW MD CD CG WG RO  MD  CD  BN                                __________________________________________________________________________     1     90 80 80 0  0  0  0  0  0  0   0   0   0                                 2     90 80 80 70 0  0  0  0  0  0   0   0   0                                 3     0  0  0  0  0  0  0  80 70 0   100 80  40                                4     0  0  0  0  0  0  0  0  0  0   100 0   0                                 5     100                                                                               80 80 60 0  0  0  80 70 70  0   0   0                                 6     80 80 80 60 100                                                                               30 20 0  0  0   0   0   0                                 7     40 40 0  0  0  0  0  0  0  0   100 0   0                                 8     0  0  0  0  0  0  0  20 0  0   0   0   10                                9     0  0  0  0  0  0  0  0  0  0   30  0   20                                10    0  0  0  0  0  0  0  0  0  0   80  0   0                                 11    0  0  0  0  0  30 0  100                                                                               95 30  100 80  40                                12    0  0  0  0  0  0  0  95 20 10  0   0   0                                 13    100                                                                               99 99 90 45 20 45 95 95 0   0   20  0                                 14    99 96 95 30 0  0  35 95 95 0   0   20  0                                 15    99 98 98 99 0  0  65 98 95 10  0   20  0                                 16    80 80 90 20 0  0  0  0  0  0   0   0   0                                 17    98 98 98 60 40 20 90 95 95 0   0   20  10                                18    95 95 90 95 0  0  85 95 95 0   0   20  10                                19    80 80 60 10 0  0  0  95 95 0   0   0   0                                 20    80 80 80 0  35 20 40 95 60 0   20  20  10                                21    0  0  0  0  0  0  0  0  0  0   10  0   0                                 22    0  0  0  0  0  0  0  0  0  0   10  0   0                                 23    0  0  0  0  0  0  0  0  0  0   50  0   0                                 24    98 40 40 0  20 10 20 95 80 0   0   30  10                                25    0  0  0  0  0  0  0  0  0  0   0   0   10                                26    0  0  0  98 60 0  0  0  0  0   0   0   0                                 27    0  0  0  0  0  0  0  0  0  0   0   0   70                                28    0  0  0  0  80 60 60 20 0  0   20  0   0                                 29    0  0  0  0  0  95 0  0  0  0   0   0   40                                30    0  0  0  0  80 60 0  0  0  0   0   0   0                                 31    0  0  0  0  98 30 40 0  0  0   0   0   0                                 32    0  0  0  0  0  0  0  40 40 0   0   0   0                                 33    95 90 80 0  50 90 0  0  0  0   0   0   0                                 34    40 90 0  0  0  20 0  0  0  0   0   0   0                                 35    0  0  0  0  0  0  0  100                                                                               60 20  0   0   0                                 36    0  0  0  0  0  0  0  90 50 20  70  0   60                                37    95 30 20 0  0  0  0  0  0  0   0   0   0                                 38    0  0  0  0  95 60 50 0  0  0   0   0   0                                 39    98 95 80 0  20 40 30 30 30 0   30  0   60                                40    0  0  0  0  80 20 0  0  0  0   0   0   0                                 41    98 98 80 0  60 20 30 0  0  0   0   0   0                                 42    0  0  20 10 100                                                                               30 20 0  0  0   0   0   0                                 43    100                                                                               99 98 0  97 70 90 100                                                                               95 30  100 40  40                                44    98 99 98 30 97 50 95 95 90 30  98  50  20                                45    98 99 95 80 70 0  40 95 80 50  90  50  40                                46    100                                                                               99 98 60 98 40 95 95 80 30  40  40  50                                47    99 99 97 30 95 30 95 95 90 40  90  60  50                                48    99 99 80 0  40 0  20 95 80 30  50  40  40                                49    100                                                                               99 98 10 97 20 70 90 80 30  50  50  50                                50    99 99 98 20 30 0  20 95 80 60  70  60  10                                51    99 98 60 70 0  0  30 98 80 20  30  40  0                                 52    98 98 50 30 50 20 60 98 80 40  40  40  50                                53    100                                                                               100                                                                               98 20 60 40 80 98 80 40  40  50  50                                54    30 0  0  0  0  0  0  0  0  0   0   0   0                                 55    90 30 30 0  95 0  0  0  0  0   0   0   0                                 56    20 10 20 0  0  0  0  0  0  0   0   0   0                                 57    98 98 98 80 80 0  30 98 70 30  0   0   40                                58    100                                                                               98 98 0  80 20 70 95 95 30  30  20  0                                 59    0  0  0  0  0  0  0  95 80 0   0   0   0                                 60    98 95 95 0  0  0  0  40 20 0   0   0   30                                61    99 98 80 80 80 20 60 98 95 95  0   0   30                                62    97 95 95 0  0  0  0  98 80 0   100 40  10                                63    100                                                                               100                                                                               100                                                                               100                                                                               80 20 100                                                                               0  0  0   0   0   0                                 64    100                                                                               100                                                                               100                                                                               95 80 10 80 0  0  0   0   0   20                                65    100                                                                               100                                                                               100                                                                               97 50 20 95 0  0  0   0   0   20                                66    100                                                                               100                                                                               100                                                                               99 98 70 98 20 0  30  0   0   20                                67    100                                                                               99 99 0  0  0  0  0  0  0   0   0   0                                 68    100                                                                               100                                                                               99 98 30 30 90 0  0  0   0   0   0                                 69    100                                                                               100                                                                               99 95 80 0  98 0  0  0   0   0   0                                 70    100                                                                               100                                                                               99 20 30 20 40 40 0  0   10  0   20                                71    100                                                                               100                                                                               99 0  0  20 30 0  0  0   20  30  30                                72    100                                                                               95 90 30 0  0  0  0  0  0   0   0   0                                 73    100                                                                               90 95 40 0  0  0  0  0  0   0   0   0                                 74    100                                                                               98 98 10 20 0  0  90 40 20  20  0   30                                75    100                                                                               100                                                                               100                                                                               50 99 50 80 98 98 20  20  30  40                                76    100                                                                               100                                                                               100                                                                               20 95 20 0  98 90 0   0   20  10                                77    100                                                                               99 99 0  80 10 20 90 60 0   0   0   30                                78    100                                                                               98 98 0  10 20 0  30 30 0   0   0   20                                79    100                                                                               100                                                                               100                                                                               20 80 20 90 0  0  0   0   0   10                                80    80 40 95 0  0  0  0  0  0  0   0   0   0                                 81    100                                                                               100                                                                               100                                                                               0  98 80 90 95 60 0   10  20  30                                82    100                                                                               99 99 0  95 40 70 80 80 0   20  20  40                                83    100                                                                               100                                                                               100                                                                               10 98 40 98 95 80 20  30  40  40                                84    100                                                                               100                                                                               99 10 80 50 95 95 90 0   20  30  40                                85    0  0  0  0  0  0  0  0  0  0   10  0   0                                 86    98 98 80 0  30 0  10 90 70 10  30  20  40                                87    98 98 50 0  0  0  0  95 80 10  30  30  40                                88    100                                                                               100                                                                               95 0  70 0  20 95 80 0   10  30  40                                89    100                                                                               99 95 0  20 0  0  95 10 0   30  30  40                                90    98 20 20 0  0  0  0  60 0  0   70  20  20                                91    100                                                                               100                                                                               100                                                                               90 99 95 95 98 95 60  80  80  80                                92    100                                                                               100                                                                               100                                                                               70 98 90 95 95 80 40  60  80  40                                93    100                                                                               100                                                                               100                                                                               92 98 95 98 98 80 80  95  95  80                                94    100                                                                               100                                                                               99 20 90 90 98 95 98 90  98  95  80                                95    100                                                                               100                                                                               99 30 95 80 90 95 80 80  70  80  70                                96    100                                                                               100                                                                               99 20 95 40 90 95 80 20  40  80  40                                97    100                                                                               98 40 0  95 0  0  98 80 20  20  80  30                                98    100                                                                               99 99 20 97 10 60 95 60 0   10  80  30                                99    100                                                                               98 98 20 60 30 50 95 80 10  40  80  40                                100   100                                                                               100                                                                               100                                                                               80 95 10 80 98 80 0   0   90  40                                101   100                                                                               98 99 30 98 10 50 99 70 10  40  80  30                                102   99 99 97 20 98 0  20 98 95 0   30  80  40                                103   99 98 95 60 99 30 70 95 70 20  10  30  40                                104   90 50 40 20 10 0  0  0  10 0   10  0   0                                 105   99 30 20 10 98 0  0  0  0  0   10  0   0                                 106   100                                                                               100                                                                               99 20 95 40 50 98 90 40  100 60  30                                107   95 90 80 10 0  0  0  70 0  0   0   30  0                                 108   98 97 97 20 98 10 30 99 60 10  20  30  40                                109   0  0  0  0  0  0  0  80 10 0   30  0   0                                 110   100                                                                               50 80 30 0  0  0  30 0  0   10  0   0                                 111   95 40 70 20 95 0  0  0  0  0   20  0   0                                 112   98 40 40 0  60 0  0  0  0  0   10  0   0                                 113   70 20 20 0  0  10 0  0  0  0   0   0   0                                 114   100                                                                               99 99 97 40 0  70 98 90 10  0   60  40                                115   100                                                                               99 99 40 30 20 80 98 95 80  0   100 40                                116   99 98 98 70 20 20 40 98 95 0   10  40  40                                117   100                                                                               98 98 60 10 20 10 95 60 10  30  100 50                                118   99 98 95 0  0  0  0  98 30 20  0   0   30                                119   98 98 95 30 0  0  0  98 10 0   0   30  10                                120   99 97 98 30 20 0  10 98 80 20  0   50  40                                121   100                                                                               98 97 80 0  0  0  99 98 30  0   98  30                                122   0  0  0  0  0  100                                                                               0  0  0  0   100 0   0                                 123   30 0  30 30 60 30 40 90 70 10  0   0   0                                 124   99 97 98 80 0  0  40 70 30 0   0   0   0                                 125   100                                                                               100                                                                               100                                                                               100                                                                               98 80 60 98 90 20  30  98  60                                126   100                                                                               100                                                                               100                                                                               99 98 80 95 98 90 30  30  60  60                                127   -- 100                                                                               100                                                                               99 99 95 99 -- 90 0   40  40  40                                128   -- 100                                                                               100                                                                               99 98 95 99 -- 80 10  40  40  40                                129   -- 100                                                                               100                                                                               95 98 40 98 -- 40 0   0   0   10                                130   -- 100                                                                               99 95 80 0  95 -- 40 0   0   40  30                                131   -- 95 98 20 80 60 70 -- 0  0   0   0   10                                132   -- 100                                                                               99 90 30 20 70 -- 0  0   0   0   20                                133   -- 90 98 30 0  0  0  -- 0  0   0   0   0                                 134   -- 100                                                                               100                                                                               99 95 20 40 -- 40 10  0   0   30                                135   -- 0  0  0  0  0  0  -- 0  0   0   0   10                                136   -- 98 95 10 0  0  0  -- 0  0   0   0   0                                 137   -- 40 40 0  0  0  0  -- 0  0   0   0   0                                 138   -- 95 98 40 80 20 0  -- 70 0   0   0   0                                 139   -- 96 97 60 0  0  0  -- 0  0   0   0   0                                 140   -- 99 98 40 0  0  0  -- 0  0   0   0   0                                 141   -- 98 98 30 80 0  0  -- 40 0   0   0   20                                142   -- 100                                                                               100                                                                               40 30 0  0  -- 70 0   0   0   0                                 143   -- 100                                                                               100                                                                               40 30 10 0  -- 40 0   0   0   20                                144   -- 100                                                                               100                                                                               100                                                                               98 98 95 -- 80 0   30  0   30                                145   -- 100                                                                               100                                                                               97 95 95 98 -- 80 0   0   0   40                                146   -- 80 95 10 0  0  0  -- 0  0   0   0   0                                 147   -- 30 40 0  0  0  0  -- 0  0   0   0   0                                 148   -- 100                                                                               100                                                                               97 98 97 99 -- 85 20  70  40  20                                149   -- 100                                                                               100                                                                               97 98 97 99 -- 80 0   30  0   70                                150   -- 100                                                                               100                                                                               40 40 30 0  -- 60 0   30  0   0                                 151   -- 100                                                                               100                                                                               10 0  0  0  -- 75 0   30  0   50                                152   -- 100                                                                               99 70 20 0  0  -- 60 0   30  0   0                                 153   -- 100                                                                               100                                                                               98 40 30 80 -- 95 0   40  0   60                                154   -- 100                                                                               100                                                                               40 10 50 60 -- 20 0   0   0   30                                155   -- 100                                                                               100                                                                               70 90 90 90 -- 20 0   20  0   20                                156   -- 0  0  0  0  0  0  -- 30 0   0   0   20                                157   -- 100                                                                               100                                                                               80 80 80 98 -- 95 40  70  60  30                                158   -- 100                                                                               100                                                                               98 98 98 98 -- 95 0   30  0   50                                159   -- 40 50 20 0  0  0  -- 0  0   0   0   0                                 160   -- 98 100                                                                               40 30 10 80 -- 0  0   0   0   0                                 161   -- 100                                                                               100                                                                               95 40 50 0  -- 85 10  70  0   0                                 162   -- 100                                                                               100                                                                               100                                                                               0  80 20 -- 90 20  0   0   40                                163   -- 100                                                                               100                                                                               0  20 20 0  -- 20 0   0   0   0                                 164   -- 100                                                                               100                                                                               20 0  0  0  -- 80 0   20  20  0                                 165   -- 100                                                                               100                                                                               100                                                                               50 70 20 -- 30 20  10  0   0                                 166   -- 100                                                                               100                                                                               100                                                                               80 80 80 -- 90 30  0   0   40                                167   -- 90 70 0  0  0  0  -- 0  0   0   0   0                                 168   -- 80 70 0  0  0  0  -- 0  0   0   0   20                                169   -- 100                                                                               98 30 40 0  40 -- 95 0   30  80  50                                170   -- 100                                                                               99 40 50 30 50 -- 95 20  20  40  60                                171   -- 98 98 98 0  0  0  -- 60 0   0   0   0                                 172   -- 98 98 40 0  0  0  -- 70 0   0   0   0                                 173   -- 95 30 0  0  0  0  -- 20 0   0   0   0                                 174   -- 98 60 20 0  0  0  -- 40 0   0   0   10                                175   -- 98 98 30 0  0  0  -- 60 10  0   0   0                                 176   -- 99 98 80 40 0  20 -- 70 10  0   0   10                                177   -- 100                                                                               100                                                                               20 90 30 20 -- 98 20  10  10  20                                178   -- 98 98 30 97 0  20 -- 90 30  0   0   0                                 179   -- 98 70 0  0  0  0  -- 60 0   0   0   0                                 180   -- 99 99 10 80 20 30 -- 95 0   20  40  0                                 181   -- 30 50 20 90 100                                                                               0  -- 90 98  100 100 100                               182   -- 100                                                                               100                                                                               80 40 30 70 -- 0  0   0   0   0                                 __________________________________________________________________________     Percent Control at 2 lb/A                                                      Compound                                                                             Pre-emergence        Post-emergence                                      Number                                                                               CG FT WG WO MD CD PW CG FT WG WO MD CD PW                                __________________________________________________________________________     183   -- 80 98 80 10 0  10 -- 80 80 20 20 0  10                                184   -- 100                                                                               100                                                                               100                                                                               10 98 90 -- 99 95 70 100                                                                               98 100                               185   -- 100                                                                               100                                                                               100                                                                               98 99 100                                                                               -- 80 90 20 20 30 0                                 186   -- 20 10 10 0  0  0  -- 0  0  0  0  0  0                                 187   -- 100                                                                               100                                                                               10 0  20 0  -- 80 90 10 50 50 20                                188   -- 99 96 80 0  0  0  -- 20 20 0  0  0  0                                 189   -- 100                                                                               98 40 0  0  0  -- 50 40 0  0  0  0                                 190   -- 0  20 0  0  0  0  -- 0  0  0  0  0  0                                 191   -- 98 98 20 0  40 0  -- 60 80 0  0  0  0                                 192   -- 100                                                                               100                                                                               80 20 80 60 -- 80 80 10 0  0  0                                 193   -- 100                                                                               100                                                                               60 0  0  0  -- 30 40 0  0  0  0                                 194   -- 20 60 0  0  0  0  -- 0  0  0  0  0  0                                 195   -- 20 60 0  0  0  0  -- 0  0  0  0  0  0                                 196   -- 0  0  0  0  0  0  -- 20 0  0  0  0  0                                 197   -- 10 10 0  0  0  0  -- 0  0  0  0  0  0                                 198   -- 40 60 0  0  0  0  -- 20 20 0  0  0  0                                 199   -- 100                                                                               100                                                                               70 20 98 40 -- 90 90 30 40 40 30                                200   -- 0  0  0  0  0  0  -- 80 60 0  10 70 20                                201   -- 30 80 10 0  0  0  -- 80 80 20 30 30 10                                202   -- 0  0  0  0  0  0  -- 80 40 0  20 70 40                                203   -- 100                                                                               100                                                                               98 30 98 0  -- 90 80 20 30 50 50                                204   -- 100                                                                               100                                                                               90 30 80 0  -- 90 80 20 30 60 0                                 205   -- 100                                                                               100                                                                               80 0  90 98 -- 70 80 20 20 30 20                                206   -- 100                                                                               100                                                                               80 95 98 30 -- 80 80 10 30 20 100                               207   -- 100                                                                               100                                                                               80 60 100                                                                               100                                                                               -- 80 80 80 40 60 20                                208   -- 100                                                                               100                                                                               60 20 100                                                                               100                                                                               -- 80 60 0  0  0  0                                 209   -- 40 0  0  50 60 90 -- 0  0  40 40 60 40                                210   -- 100                                                                               100                                                                               100                                                                               60 100                                                                               100                                                                               -- 0  0  0  0  0  0                                 211   -- 98 98 70 0  80 80 -- 60 40 50 60 75 60                                212   -- 70 50 0  0  40 0  -- 60 0  0  70 70 60                                __________________________________________________________________________     Percent Control at 8 lb/A                                                      Compound                                                                             Pre-emergence        Post-emergence                                      Number                                                                               CG FT WG RO PW MD CD CG WG RO  MD  CD  BN                                __________________________________________________________________________     213   98 99 99 40 0  0  40 95 95 20  10  20  30                                214   100                                                                               100                                                                               100                                                                               20 90 30 85 95 90 0   0   20  50                                215   100                                                                               100                                                                               100                                                                               98 80 60 95 100                                                                               95 20  0   0   50                                216   100                                                                               100                                                                               100                                                                               60 80 30 80 100                                                                               95 0   0   0   40                                217   100                                                                               99 99 50 90 10 60 0  0  0   0   0   0                                 218   100                                                                               99 99 99 90 10 80 90 80 0   0   0   20                                219   100                                                                               100                                                                               100                                                                               100                                                                               90 60 80 95 90 20  0   0   0                                 220   100                                                                               100                                                                               100                                                                               98 98 20 90 20 0  0   60  0   20                                221   100                                                                               100                                                                               100                                                                               70 90 60 95 98 90 0   20  30  50                                222   100                                                                               100                                                                               100                                                                               98 99 97 98 95 80 70  40  80  98                                223   99 97 98 60 30 0  60 100                                                                               90 0   0   100 40                                224   100                                                                               98 98 95 50 30 40 98 90 20  10  40  40                                225   100                                                                               99 95 60 30 0  40 98 95 20  10  40  40                                226   98 98 80 0  0  0  0  98 30 0   30  40  50                                227   98 98 30 0  0  0  0  80 20 0   0   0   40                                228   98 98 95 20 0  0  0  98 30 0   0   0   30                                229   99 98 98 98 0  0  0  99 90 30  0   50  30                                230   98 80 80 80 0  0  0  98 90 10  0   100 40                                231   0  0  0  0  0  0  0  90 0  0   0   0   0                                 232   98 96 98 97 0  0  0  95 70 20  0   30  30                                233   100                                                                               100                                                                               100                                                                               98 70 70 60 98 80 10  40  20  40                                234   100                                                                               100                                                                               100                                                                               99 99 95 90 98 95 20  30  100 80                                235   -- 100                                                                               100                                                                               95 90 95 99 -- 80 10  50  60  20                                236   -- 100                                                                               100                                                                               99 99 96 99 -- 85 20  40  40  50                                237   -- 99 99 40 95 30 95 -- 60 0   0   0   5                                 238   -- 100                                                                               100                                                                               95 40 30 90 -- 80 0   0   40  40                                239   -- 95 98 20 80 60 70 -- 0  0   0   0   10                                240   -- 100                                                                               100                                                                               95 40 60 90 -- 30 0   0   100 40                                241   -- 80 95 0  0  0  0  -- 0  0   0   0   10                                242   -- 100                                                                               100                                                                               98 95 10 80 -- 30 0   0   0   30                                243   -- 0  10 10 0  0  0  -- 0  0   0   0   10                                244   -- 40 40 0  0  0  0  -- 0  0   0   0   0                                 245   -- 95 95 10 0  0  0  -- 0  0   0   0   0                                 246   -- 90 98 20 60 0  0  -- 60 0   0   30  0                                 247   -- 99 95 40 30 0  0  -- 0  0   0   0   0                                 248   -- 30 0  0  0  0  0  -- 0  0   0   0   0                                 249   -- 98 98 40 0  0  0  -- 40 0   0   0   10                                250   -- 99 100                                                                               0  30 40 40 -- 60 0   0   0   0                                 251   -- 98 97 40 0  0  0  -- 60 0   0   0   40                                252   -- 100                                                                               100                                                                               98 80 90 97 -- 70 0   40  0   20                                253   -- 100                                                                               100                                                                               100                                                                               98 98 98 -- 70 0   30  0   40                                254   -- 80 70 30 0  0  0  -- 0  0   0   0   0                                 255   -- 80 70 40 0  0  0  -- 20 0   0   0   40                                256   -- 100                                                                               100                                                                               99 98 98 98 -- 80 0   40  30  30                                257   -- 100                                                                               100                                                                               100                                                                               99 98 98 -- 70 0   30  0   50                                258   -- 100                                                                               100                                                                               30 0  0  0  -- 40 0   0   0   0                                 259   -- 100                                                                               100                                                                               30 20 0  0  -- 70 0   30  0   50                                260   -- 100                                                                               100                                                                               50 80 60 80 -- 60 0   30  0   30                                261   -- 100                                                                               100                                                                               40 60 50 30 -- 70 0   20  0   60                                262   -- 100                                                                               100                                                                               60 80 60 95 -- 0  0   0   0   30                                263   -- 100                                                                               100                                                                               70 90 90 95 -- 30 0   0   0   20                                264   -- 0  40 10 0  0  0  -- 0  0   0   0   0                                 265   -- 98 98 97 0  0  0  -- 0  0   0   0   0                                 266   -- 100                                                                               100                                                                               98 80 80 98 -- 80 0   50  0   30                                267   -- 100                                                                               100                                                                               90 60 80 95 -- 80 0   50  0   60                                268   -- 70 80 40 0  0  0  -- 0  0   0   0   0                                 269   -- 80 90 10 30 0  20 -- 0  0   0   0   0                                 270   -- 0  70 0  0  0  0  -- 0  0   0   0   0                                 271   -- 100                                                                               100                                                                               100                                                                               50 90 50 -- 80 20  0   0   30                                272   -- 100                                                                               95 20 0  0  0  -- 0  0   0   0   0                                 273   -- 100                                                                               100                                                                               30 0  0  0  -- 40 0   70  0   0                                 274   -- 95 90 80 50 70 20 -- 0  0   0   0   0                                 275   -- 100                                                                               100                                                                               100                                                                               80 80 80 -- 80 20  10  10  0                                 276   -- 50 0  0  0  0  0  -- 0  0   0   0   0                                 277   -- 99 98 10 40 0  40 -- 80 20  10  10  30                                278   -- 99 96 30 0  0  0  -- 70 10  0   0   50                                279   -- 98 98 30 0  0  0  -- 0  0   0   0   0                                 280   -- 60 95 20 0  0  0  -- 0  0   0   0   0                                 281   -- 95 10 0  0  0  0  -- 50 0   0   0   0                                 282   -- 20 0  0  0  0  0  -- 0  0   0   0   0                                 283   -- 100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               100                                                                               -- 90 60  100 90  100                               284   -- 100                                                                               100                                                                               100                                                                               100                                                                               99 99 -- 90 60  80  100 30                                __________________________________________________________________________     Percent Control at 2 lb/A                                                      Compound                                                                             Pre-emergence        Post-emergence                                      Number                                                                               CG FT WG WO MD CD PW CG FT WG WO MD CD PW                                __________________________________________________________________________     285   -- 100                                                                               100                                                                               30 10 90 60 -- 90 90 40 40 40 0                                 286   -- 100                                                                               40 10 80 80 20 -- 40 40 20 80 70 0                                 287   -- 100                                                                               100                                                                               95 95 100                                                                               100                                                                               -- 98 70 60 75 70 100                               288   -- 100                                                                               100                                                                               100                                                                               85 100                                                                               100                                                                               -- 75 80 75 60 70 0                                 289   -- 100                                                                               100                                                                               98 80 100                                                                               100                                                                               -- 60 70 50 40 75 0                                 290   -- 100                                                                               100                                                                               98 98 100                                                                               100                                                                               -- 65 70 50 40 60 30                                291   -- 100                                                                               100                                                                               100                                                                               95 100                                                                               100                                                                               -- 75 75 60 30 60 0                                 292   -- 100                                                                               100                                                                               100                                                                               95 100                                                                               100                                                                               -- 70 75 60 60 70 50                                293   -- 100                                                                               100                                                                               100                                                                               98 100                                                                               100                                                                               -- 80 75 60 60 60 30                                294   -- 100                                                                               100                                                                               95 90 100                                                                               100                                                                               -- 70 75 75 60 60 100                               __________________________________________________________________________

For practical use as herbicides the compounds of this invention are generally incorporated into herbicidal compositions which comprise an inert carrier and a herbicidally toxic amount of such a compound. Such herbicidal compositions, which can also be called formulations, enable the active compound to be applied conveniently to the site of the weed infestation in any desired quantity.

Useful formulations of the compounds of the present invention can be prepared in conventional ways. They include dusts, granules, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates and the like. Many of these may be applied directly. Sprayable formulations can be extended in suitable media and used at spray volume of from a few liters to several hundred liters per hectare. High strength compositions are pri:aarily used as intermediates for further formulation. The formulations, broadly, contain about 1% to 99% by weight of active ingredient(s) and at least one of (a) about 0.1% to 20% surfactant(s) and (b) about 5% to 99% solid or liquid diluent(s). More specifically, they will contain these ingredients in the following approximate proportions:

    ______________________________________                                                    Percent by Weight                                                              Active                                                                         Ingredient                                                                             Diluent(s) Surfactant(s)                                    ______________________________________                                         Wettable Powders                                                                            20-90      0-74      1-10                                         Oil Suspensions,                                                                            5-50      40-95      0-15                                         Emulsions, Solutions                                                           (including Emulsifi-                                                           able Concentrates)                                                             Aqueous Suspensions                                                                         10-50     40-84      1-20                                         Dusts        1-25      70-99      0-5                                          Granules and Pellets                                                                        1-95       5-99      0-15                                         High Strength                                                                               90-99      0-10      0-2                                          Compositions                                                                   ______________________________________                                    

Lower or high levels of active ingredient can, of course, be present depending on the intended use and the physical properties of the compound. Higher ratios of surfactant to active ingredient are sometimes desirable, and are achieved by incorporation into the formulation or by tank mixing.

Compositions including active compounds also may be applied by addition to irrigation waters supplied to the field to be treated. This method of application permits penetration of the compounds into the soil as the water is absorbed therein. Compositions applied to the surface of the soil can be incorporated and distributed below the surface of the soil by conventional means such as discing or mixing operations.

The compositions can also comprise such additional Substances as other pesticides, such as insecticides, nematocides, fungicides, and the like; stabilizers, spreaders, deactivators, adhesives, stickers, fertilizers, activators, synergists, antidotes, and the like.

The compounds of the present invention are also useful when combined with other herbicides and/or defoliants, dessicants, growth inhibitors, and the like in the herbicidal compositions heretofore described. These other materials can comprise from about 5% to about 95% of the active ingredients in the herbicidal compositions. Use of combinations of these other herbicides and/or defoliants, dessicants, etc. with the compounds of the present invention provide herbicidal compositions which are more effective in controlling weeds and often provide results unattainable with separate compositions of the individual herbicides.

The other herbicides, defoliants, dessicants and plant growth inhibitors, with which the compounds of this invention can be used in the herbicidal compositions to control weeds, can include chlorophenoxy herbicides such as 2,4-D, 2,4,5-T, MCPA, MCPB, 4(2,4-DB), 2,4-DEB, 4-CPB, 4-CPA, 4-CPP, 2,4,5-TB, 2,4,5-TES, 3,4-DA, silvex and the like; carbamate herbicides such as IPC, CIPC, swep, barban, BCPC, CEPC, CPPC, and the like; thiocarbamate and dithiocarbamate herbicides such as CDEC, metham sodium, EPTC, diallate, PEBC, perbulate, vernolate and the like; substituted urea herbicides such as norea, sifuron, dichloral urea, chloroxuron, cycluron, fenuron, monuron, monuron TCA, diuron, linuron, monolinuron neburon, buturon, trimethuron and the like; symmetrical triazine herbicides such as simazine, chlorazine, atraone, desmetryne, norazine, ipazine, prometryn, atazine, trietazine, simetone, prometone, propazine, ametryne and the like; chloroacetamide herbicides such as 4-(chloroacetyl)morpholine, 1-(chloroacetyl)-piperidine and the like; chlorinated aliphatic acid herbicides such as TCA, dalapon, 2,3-dichloropropionic acid, 2,2,3-TPA and the like; chlorinated benzoic acid and phenylacetic acid herbicides such as 2,3,6-TBA, 2,3,5,6-TBA, dicamba, tricamba, amiben, fenac, PBA, 2-methoxy-3,6-dichlorophenylacetic acid, 3-methoxy-2,6-dichlorophenylacetic acid, 2-methoxy-3,5,6-trichlorophenylacetic acid, 2,4-dichloro-3-nitrobenzoic acid and the like; and such compounds as aminotriazole, maleic hydrazide, phenyl mercuric acetate, endothal, biuret, technical chlordane, dimethyl 2,3,5,6-tetrachloroterephthalate, diquat, erbon, DNC, DNBP, dichlobenil, DPA, diphenamide, dipropalin, trifluralin, solan, dicryl, merphos, DMPA, DSMA, MSMA, pottasium azide, acrolein, benefin, bensulide, AMS, bromacil, 2-(3,4-dichlorophenyl)-4-methyl-1,2,4-oxazolidine-3,5-dione, bromoxynil, cacodylic acid, CMA, CPMF, cypromid, DCB, DCPA, dichlone, diphenatril, DMTT, DNAP, EBEP, EXD, HCA, ioxynil, IPX, isocil, potassium cyanate, MAA, MAMA, MCPES, MCPP, MH, molinate, NPA, OCH, paraquat, PCP, picloram, DPA, PCA, pyrichlor, sesone, terbacil, terbutol, TCBA, brominil, CP-50144, H-176-1, H-732, M-2901, planavin, sodium tetraborate, calcium cyanamid, DEF, ethyl xanthogen disulfide, sindone, sindone B, propanil and the like.

Such herbicides can also be used in the methods and compositions of this invention in the form of their salts, esters, amides, and other derivatives whenever applicable to the particular parent compounds.

Weeds are undesirable plants growing where they are not wanted, having no relative economic value, and interfering with the production of cultivated crops, with the growing of ornamental plants, or with the welfare of livestock.

Similarly, such weeds can be classified as broadleaf or grassy weeds. it is economically desirable to control the growth of such weeds without damaging beneficial plants or livestock. 

What is claimed is:
 1. A compound having the formula ##STR26## in which R₁ is hydrogen;R₂ is alkyl having 1-6 carbon atoms, inclusive; --CMAB is CHCl₂ ; X and Y are independently selected from the group consisting of lower alkyl having 1 to 6 carbon atoms, inclusive, and chloro; and Z is hydrogen.
 2. A compound according to claim 1 in whichR₁ is hydrogen; R₂ is alkyl having 1 to 6 carbon atoms, inclusive; --CMAB is --CHCl₂ ; X is chloro; Y is chloro; Z is hydrogen.
 3. A compound according to claim 2 in whichR₂ is isopropyl; X is 3-chloro; Y is 5-chloro.
 4. A compound according to claim 2 in whichR₂ is isopropyl; X is 2-chloro; Y is 3-chloro.
 5. A compound according to claim 2 in whichR₂ is ethyl; X is 3-chloro; Y is 4-chloro.
 6. A compound according to claim 2 in whichR₂ is n-propyl; X is 3-chloro; Y is 4-chloro.
 7. A compound according to claim 2 in whichR₂ is isopropyl; X is 3-chloro; Y is 4-chloro.
 8. A compound according to claim 1 in whichR₁ is hydrogen; R₂ is alkyl having 1 to 6 carbon atoms, inclusive; --CMAB is --CHCl₂ ; X is lower alkyl having 1 to 6 carbon atoms, inclusive; Y is lower alkyl having 1 to 6 carbon atoms, inclusive; Z is hydrogen.
 9. A compound according to claim 8 in whichR₂ is isopropyl; X is 3-methyl; Y is 5-methyl.
 10. A compound having the formula ##STR27## in which R₁ is hydrogen;R₂ is alkyl having 1-6 carbon atoms, inclusive; --CMAB is CHCl₂ ; X is lower alkyl having 1 to 6 carbon atoms, inclusive; Y is chloro; and Z is hydrogen.
 11. A compound according to claim 10 in whichR₂ is isopropyl; X is 2-methyl; Y is 3-chloro.
 12. A compound having the formula ##STR28## in which R₁ is allyl;R₂ is allyl; --CMAB is CHCl₂ ; X is chloro; Y is chloro; and Z is hydrogen.
 13. A compound having the formula ##STR29## in which R₁ is hydrogen;R₂ is alkyl having 1-6 carbon atoms, inclusive; --CMAB is CHF₂ ; X is chloro; Y is chloro; and Z is hydrogen.
 14. A compound according to claim 13 in whichX is 3-chloro; Y is 5-chloro; R₂ is isopropyl. 